Brominated cross-linkable polycarbonate compositions

ABSTRACT

Polymeric compositions having improved flame retardance properties are disclosed. The compositions comprise a cross-linkable polycarbonate resin having a photoactive group derived from a benzophenone, a bromine source, and optionally a non-brominated and non-chlorinated flame retardant. The composition contains a minimum amount of bromine. Articles formed from the compositions have robust flame retardance properties and enhanced chemical resistance.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a 371 of PCT Application Serial No.PCT/IB2015/054643, filed Jun. 19, 2015, which claims priority to U.S.Provisional Patent Application Ser. No. 62/014,411, filed on Jun. 19,2014, which is fully incorporated by reference.

BACKGROUND

The present disclosure relates to polymeric compositions that includecross-linkable polycarbonate resins containing a photoactive groupderived from a benzophenone and bromine. Upon exposure to ultravioletradiation, the cross-linkable polycarbonate resin will crosslink withitself and/or with other polymeric base resins also present, improvingoverall chemical resistance, flame retardance, and other characteristicsof articles formed from the polymeric compositions. Also included arearticles (e.g., sheets, films, molded components, etc.) formed from suchcompositions.

Polycarbonates (PC) are synthetic thermoplastic resins with desirableproperties such as high impact strength and toughness, heat resistance,weather and ozone resistance, and good ductility. However, such polymersdrip when exposed to a flame, and this behavior worsens as the wallthickness decreases. This behavior greatly diminishes their use intransparent and opaque thin-wall applications where a V0 or 5VA flameretardance rating is required, requiring higher loadings of flameretardance agents. Non-brominated and non-chlorinated flame retardantshave been used to improve flame retardance performance, but thisimprovement is not robust; individual samples perform well, but goodflame performance cannot be statistically predicted for multiplesamples. It would be desirable to provide articles and polymericcompositions that can perform consistently and pass applicable flameretardance tests and standards.

BRIEF DESCRIPTION

Disclosed in various embodiments herein are polymeric compositions,comprising: a cross-linkable polycarbonate resin containing aphotoactive group derived from a benzophenone; and a bromine sourcepresent in an amount such that the polymeric composition contains fromabout 0.3 wt % to about 15 wt % bromine.

The bromine source may be a brominated polymer or oligomer, or abrominated flame retardant compound. In particular embodiments, thebromine source is a brominated epoxy oligomer or is a brominated polymeror oligomer having repeating units derived from bisphenol-A andtetrabromobisphenol-A. In more specific embodiments, the brominatedpolymer or oligomer may contain repeating units derived from thetetrabromobisphenol-A in an amount such that the polymer or oligomercontains from about 5 wt % to about 30 wt % of bromine.

Alternatively, the bromine source can be selected from the groupconsisting of a polybrominated diphenyl ether (PBDE);hexabromocyclododecane (HBCD); tetrabromobisphenol-A (TTBPA);bis(2,6-dibromophenyl)-methane; 2,2-bis-(3-phenyl-4-bromophenyl)-ethane;2,2-bis-(3,5-dibromophenyl)-hexane; bis-(3-nitro-4-bromophenyl)-methane;2,2-bis-(3-bromo-4-hydroxyphenyl)-propane; 1,4-dibromobenzene;2,4′-dibromobiphenyl; and 1,2-bis(tetrabromophthalimido)ethane.

The composition may further comprise a non-brominated andnon-chlorinated flame retardant. The composition may contain from about0.06 wt % to about 0.4 wt % of the non-brominated and non-chlorinatedflame retardant. The non-brominated and non-chlorinated flame retardantmay be potassium perfluorobutane sulfonate (Rimar salt), potassiumdiphenyl sulfone-3-sulfonate (KSS), or a combination thereof.

In particular embodiments, the composition further comprises a polymericbase resin (i.e. a blend). The weight ratio of the cross-linkablepolycarbonate resin to the polymeric base resin can be from about 50:50to about 95:5. In specific embodiments, the polymeric base resin is abisphenol-A homopolycarbonate.

The composition may have a melt flow rate of about 3 to about 19 g/10minutes at 300° C./1.2 kg/360 sec dwell.

The composition may further comprise from about 0.04 wt % to about 1 wt% of a phosphite stabilizer.

In various embodiments, the cross-linkable polycarbonate resin is formedfrom a reaction comprising: a hydroxybenzophenone; a first dihydroxychain extender; and a carbonate precursor.

In some embodiments, the benzophenone is a monohydroxybenzophenone. Thecross-linkable polycarbonate resin may contain from about 0.5 mole % toabout 5 mole % of endcap groups derived from themonohydroxybenzophenone. In more particular embodiments, themonohydroxybenzophenone is 4-hydroxybenzophenone; and the firstdihydroxy chain extender is bisphenol-A. Sometimes, the reaction furthercomprises a second dihydroxy chain extender, and the polycarbonate resinis a copolymer.

In other different embodiments, the benzophenone is adihydroxybenzophenone. The cross-linkable polycarbonate resin maycontain from about 0.5 mole % to about 50 mole % of repeating unitsderived from the dihydroxybenzophenone. In specific embodiments, thedihydroxybenzophenone is 4,4′-hydroxybenzophenone; and the firstdihydroxy chain extender is bisphenol-A. Sometimes, the reaction furthercomprises an end-capping agent selected from the group consisting ofphenol, p-t-butylphenol, p-cumylphenol, octylphenol, and p-cyanophenol.

An article molded from the composition and having a thickness of 1.2 mmmay have a pFTP(V0) of at least 0.90 after exposure to 36 J/cm² of UVAradiation.

Articles formed from the polymeric compositions disclosed herein arealso disclosed. The articles may be, for example, a molded article, afilm, a sheet, a layer of a multilayer film, or a layer of a multilayersheet. The article may be formed by injection molding, overmolding,co-injection molding, extrusion, multilayer extrusion, rotationalmolding, blow molding, or thermoforming. The article may be exposed toUV radiation to cause cross-linking of the polymeric composition.

These and other non-limiting characteristics are more particularlydescribed below.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings are presented to illustrate the exemplaryembodiments disclosed herein and not to limit them.

FIG. 1 illustrates the formation of a cross-linkable polycarbonate resinfrom a dihydroxybenzophenone (4,4′-dihydroxybenzophenone), a carbonateprecursor (phosgene), a dihydroxy chain extender (bisphenol-A), and anend-capping agent (p-cumylphenol).

FIG. 2 illustrates the formation of a branched cross-linkablepolycarbonate resin from a dihydroxybenzophenone(4,4′-dihydroxybenzophenone), a carbonate precursor (phosgene), adihydroxy chain extender (bisphenol-A), an end-capping agent(p-cumylphenol), and a branching agent (1,1,1-tris-hydroxyphenylethane(THPE)).

FIG. 3 illustrates the formation of a cross-linkable polycarbonate resinfrom a monohydroxybenzophenone (4-hydroxybenzophenone), a carbonateprecursor (phosgene), and a dihydroxy chain extender (bisphenol-A).

FIG. 4 illustrates the formation of a cross-linkable polycarbonate resinfrom a monohydroxybenzophenone (4-hydroxybenzophenone), a carbonateprecursor (phosgene), a dihydroxy chain extender (bisphenol-A), and anadditional endcapping agent (p-cumylphenol).

FIG. 5 illustrates the crosslinking mechanism of the cross-linkablepolycarbonate.

DETAILED DESCRIPTION

In the following specification, the examples, and the claims whichfollow, reference will be made to some terms which are defined asfollows.

Definitions

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. All publications, patent applications,patents and other references mentioned herein are incorporated byreference in their entirety.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise.

As used in the specification and in the claims, the open-endedtransitional phrases “comprise(s),” “include(s),” “having,”“contain(s),” and variants thereof require the presence of the namedingredients/steps and permit the presence of other ingredients/steps.These phrases should also be construed as disclosing the closed-endedphrases “consist of” or “consist essentially of” that permit only thenamed ingredients/steps and unavoidable impurities, and exclude otheringredients/steps.

Numerical values used herein should be understood to include numericalvalues which are the same when reduced to the same number of significantfigures and numerical values which differ from the stated value by lessthan the experimental error of the measurement technique described fordetermining the value.

All ranges disclosed herein are inclusive of the recited endpoint andindependently combinable (for example, the range of “from 2 grams to 10grams” is inclusive of the endpoints, 2 grams and 10 grams, and all theintermediate values).

The term “about” can be used to include any numerical value that cancarry without changing the basic function of that value. When used witha range, “about” also discloses the range defined by the absolute valuesof the two endpoints, e.g., “about 2 to about 4” also discloses therange “from 2 to 4.” The term “about” may refer to plus or minus 10% ofthe indicated number.

Compounds are described using standard nomenclature. Any position notsubstituted by an indicated group is understood to have its valencyfilled by a bond or a hydrogen atom. A dash (“-”) that is not betweentwo letters indicates a point of attachment for a substituent, e.g. —CHOattaches through the carbon atom.

The term “aliphatic” refers to an array of atoms that is not aromatic.The backbone of an aliphatic group is composed exclusively of carbon. Analiphatic group is substituted or unsubstituted. Exemplary aliphaticgroups are ethyl and isopropyl.

An “aromatic” radical has a ring system containing a delocalizedconjugated pi system with a number of pi-electrons that obeys Hückel'sRule. The ring system may include heteroatoms (e.g. N, S, Se, Si, O), ormay be composed exclusively of carbon and hydrogen. Aromatic groups arenot substituted. Exemplary aromatic groups include phenyl, thienyl,naphthyl, and biphenyl.

An “ester” radical has the formula —CO—O—, with the carbon atom and theoxygen atom both bonded to carbon atoms. A “carbonate” radical has theformula —O—CO—O—, with the oxygen atoms both bonded to carbon atoms.Note that a carbonate group is not an ester group, and an ester group isnot a carbonate group.

A “hydroxyl” radical has the formula —OH, with the oxygen atom bonded toa carbon atom. A “carboxy” or “carboxyl” radical has the formula —COOH,with the carbon atom bonded to another carbon atom. A carboxyl group canbe considered as having a hydroxyl group. However, please note that acarboxyl group participates in certain reactions differently from ahydroxyl group. An “anhydride” radical has the formula —CO—O—CO—, withthe carbonyl carbon atoms bonded to other carbon atoms. This radical canbe considered equivalent to two carboxyl groups. The term “acid halide”refers to a radical of the formula —CO—X, with the carbon atom bonded toanother carbon atom.

The term “alkyl” refers to a fully saturated radical composed entirelyof carbon atoms and hydrogen atoms. The alkyl radical may be linear,branched, or cyclic. The term “aryl” refers to an aromatic radicalcomposed exclusively of carbon and hydrogen. Exemplary aryl groupsinclude phenyl, naphthyl, and biphenyl. The term “hydrocarbon” refers toa radical which is composed exclusively of carbon and hydrogen. Bothalkyl and aryl groups are considered hydrocarbon groups. The term“heteroaryl” refers to an aromatic radical containing at least oneheteroatom. Note that “heteroaryl” is a subset of aromatic, and isexclusive of “aryl”.

The term “halogen” refers to fluorine, chlorine, bromine, and iodine.The term “halo” means that the substituent to which the prefix isattached is substituted with one or more independently selected halogenradicals.

The term “alkoxy” refers to an alkyl radical which is attached to anoxygen atom, i.e. —O—C_(n)H_(2n+1). The term “aryloxy” refers to an arylradical which is attached to an oxygen atom, e.g. —O—C₆H₅.

An “alkenyl” radical is composed entirely of carbon atoms and hydrogenatoms and contains a carbon-carbon double bond that is not part of anaromatic structure. An exemplary alkenyl radical is vinyl (—CH═CH₂).

The term “alkenyloxy” refers to an alkenyl radical which is attached toan oxygen atom, e.g. —O—CH═CH₂. The term “arylalkyl” refers to an arylradical which is attached to an alkyl radical, e.g. benzyl (—CH₂—C₆H₅).The term “alkylaryl” refers to an alkyl radical which is attached to anaryl radical, e.g. tolyl (—C₆H₄—CH₃).

The term “substituted” refers to at least one hydrogen atom on the namedradical being substituted with another functional group, such ashalogen, —CN, or —NO₂. However, the functional group is not hydroxyl,carboxyl, ester, acid halide, or anhydride. Besides the aforementionedfunctional groups, an aryl group may also be substituted with alkyl oralkoxy. An exemplary substituted aryl group is methylphenyl.

The term “copolymer” refers to a molecule derived from two or morestructural unit or monomeric species, as opposed to a homopolymer, whichis derived from only one structural unit or monomer.

The terms “Glass Transition Temperature” or “Tg” refer to the maximumtemperature that a polycarbonate will retain at least one usefulproperty such as impact resistance, stiffness, strength, or shaperetention. The Tg can be determined by differential scanningcalorimetry.

The term “haze” refers to the percentage of transmitted light, which inpassing through a specimen deviates from the incident beam by forwardscattering. Percent (%) haze may be measured according to ASTM D1003-13.

The term “Melt Volume Rate” (MVR) or “Melt Flow Rate (MFR)” refers tothe flow rate of a polymer in a melt phase as determined using themethod of ASTM D1238-13. MVR is expressed in cubic centimeter per 10minutes, and MFR is expressed in grams per 10 minutes. The higher theMVR or MFR value of a polymer at a specific temperature, the greater theflow of that polymer at that specific temperature.

The term “percent light transmission” or “% T” refers to the ratio oftransmitted light to incident light, and may be measured according toASTM D1003-13.

“Polycarbonate” as used herein refers to an oligomer or a polymercomprising residues of one or more monomers, joined by carbonatelinkages.

The terms “UVA”, “UVB”, “UVC”, and “UVV” as used herein were defined bythe wavelengths of light measured with the radiometer (EIT PowerPuck)used in these studies, as defined by the manufacturer (EIT Inc.,Sterling, Va.). “UV” radiation refers to wavelengths of 200 nanometers(nm) to 450 nm. UVA refers to the range from 320-390 nm, UVB to therange from 280-320 nm, UVC to the range from 250-260 nm, and UVV to therange from 395-445 nm.

The term “crosslink” and its variants refer to the formation of a stablecovalent bond between two polymers/oligomers. This term is intended toencompass the formation of covalent bonds that result in networkformation, or the formation of covalent bonds that result in chainextension. The term “cross-linkable” refers to the ability of apolymer/oligomer to initiate the formation of such stable covalentbonds.

The present disclosure refers to “polymers,” “oligomers”, and“compounds”. A polymer is a large molecule composed of multiplerepeating units chained together. Different molecules of a polymer willhave different lengths, and so a polymer has a molecular weight that isbased on the average value of the molecules (e.g. weight average ornumber average molecular weight). An “oligomer” has only a few repeatingunits, while a “polymer” has many repeating units. In this disclosure,“oligomer” refers to molecules having a weight average molecular weight(Mw) of less than 15,000, and the term “polymer” refers to moleculeshaving an Mw of 15,000 or more, as measured by GPC using polycarbonatemolecular weight standards, measured prior to any UV exposure. In acompound, all molecules have the same molecular weight. Molecularweights are reported herein in Daltons or g/mol.

Polymeric Compositions

The present disclosure relates to polymeric compositions containing aphotoactive additive and also containing a bromine source in a specifiedamount. The compositions may also include one or more polymeric baseresins. More particularly, the photoactive additive is a cross-linkablepolycarbonate resin having a photoactive group derived from abenzophenone. When the composition is exposed to the appropriatewavelength(s) of light, the resulting composition will have improvedanti-drip and flame retardant properties compared to the base resinsalone or to the composition prior to the UV irradiation. Thecompositions, blended or neat, can be used to provide thin-walledmaterials that are UL94 V0 compliant and highly transparent. Thecross-linkable polycarbonate resins are discussed first, then thebromine sources are discussed.

Generally, the photoactive additives (PAA) of the present disclosure arecross-linkable polycarbonate resins that contain photoactive ketonegroups. The term “photoactive” refers to a moiety that, when exposed toultraviolet light of the appropriate wavelength, crosslinks with anothermolecule. For example, the bisphenol-A monomer in a bisphenol-Ahomopolycarbonate is not considered to be photoactive, even thoughphoto-Fries rearrangement can occur, because the atoms do not crosslink,but merely rearrange in the polymer backbone. A “ketone group” is acarbonyl group (—CO—) that is bonded to two other carbon atoms (i.e.—R—CO—R′—). An ester group and a carboxylic acid group are not a ketonegroup because their carbonyl group is bonded to an oxygen atom.

The photoactive additive is formed from a reaction mixture containing atleast a benzophenone, a dihydroxy chain extender, and a carbonateprecursor. The benzophenone has either one or two phenolic groups, andprovides a photoactive ketone group for crosslinking. The benzophenoneprovides a photoactive ketone group for crosslinking. The carbonateprecursor forms carbonate linkages between the dihydroxy compounds. Thereaction product of this mixture is the photoactive additive, which inparticular embodiments is a cross-linkable polycarbonate resin. Thebenzophenone can be either a monohydroxybenzophenone that acts as anend-capping agent, or can be a dihydroxybenzophenone monomer. Asdesired, an end-capping agent and/or additional dihydroxy chainextenders can also be included. The additional end-capping agent and thedihydroxy chain extender(s) do not have photoactive properties.

In some embodiments, the benzophenone is a monohydroxybenzophenone, andhas the structure of Formula (I):

In more specific embodiments, the monohydroxybenzophenone is4-hydroxybenzophenone (4-HBP).

In other embodiments, the benzophenone is a dihydroxybenzophenone, andhas the structure of Formula (II):

The two hydroxyl groups can be located in any combination of locations,e.g. 4,4′-; 2,2′-; 2,4′-; etc. In more specific embodiments, thedihydroxybenzophenone is 4,4′-dihydroxybenzophenone (4,4′-DHBP).

The cross-linkable polycarbonate resins also include one or moredihydroxy chain extenders (depending on whether a homopolymer, copolymeror terpolymer is desired). The dihydroxy chain extender is a moleculethat contains only two hydroxyl groups. It is contemplated that thedihydroxy chain extender can be a diol or a diacid. The dihydroxy chainextender is not photoactive when exposed to light. The chain extendercan be used to provide a desired level of miscibility when the additiveis mixed with other polymeric resins. The photoactive additive maycomprise from about 75 mole % to about 99.5 mole %, or from 95 mole % toabout 99 mole %, or from about 80 mole % to about 95 mole %, or fromabout 80 mole % to about 90 mole %, of the dihydroxy chain extender.

A first exemplary dihydroxy chain extender is a bisphenol of Formula(A):

wherein R^(a) and R^(b) each represent a halogen atom or a monovalenthydrocarbon group and may be the same or different; p and q are eachindependently integers of 0 to 4;and A represents one of the groups of Formula (A-1):

wherein R^(c) and R^(d) each independently represent a hydrogen atom ora monovalent linear or cyclic hydrocarbon group; R^(e) is a divalenthydrocarbon group; R^(f) is a monovalent linear hydrocarbon group; and ris an integer from 0 to 5. For example, A can be a substituted orunsubstituted C₃-C₁₈ cycloalkylidene.

Specific examples of the types of bisphenol compounds that may berepresented by Formula (A) include 2,2-bis(4-hydroxyphenyl) propane(“bisphenol-A” or “BPA”), 4,4′-(1-phenylethane-1,1-diyl)diphenol or1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol-AP);1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane) (bisphenol TMC);1,1-bis(4-hydroxy-3-methylphenyl) cyclohexane (DMBPC); and2,2-bis(3,5-dibromo-4-hydroxyphenyl) propane (tetrabromobisphenol-A orTBBPA).

A second exemplary dihydroxy chain extender is a bisphenol of Formula(B):

wherein each R^(k) is independently a C₁₋₁₀ hydrocarbon group, and n is0 to 4. The halogen is usually bromine. Examples of compounds that maybe represented by Formula (B) include resorcinol, 5-methyl resorcinol,5-phenyl resorcinol, catechol; hydroquinone; and substitutedhydroquinones such as 2-methyl hydroquinone.

A third exemplary dihydroxy chain extender is abisphenolpolydiorganosiloxane of Formula (C-1) or (C-2):

wherein each Ar is independently aryl; each R is independently alkyl,alkoxy, alkenyl, alkenyloxy, aryl, aryloxy, arylalkyl, or alkylaryl;each R₆ is independently a divalent C₁-C₃₀ organic group such as aC₁-C₃₀ alkyl, C₁-C₃₀ aryl, or C₁-C₃₀ alkylaryl; and D and E are anaverage value of 2 to about 1000, including from about 2 to about 500,or about 10 to about 200, or more specifically about 10 to about 75.

Specific examples of Formulas (C-1) and (C-2) are illustrated below asFormulas (C-a) through (C-d):

where E is an average value from 10 to 200.

A fourth exemplary dihydroxy chain extender is an aliphatic diol ofFormula (D):

wherein each X is independently hydrogen, halogen, or alkyl; and j is aninteger from 1 to 20. Examples of an aliphatic diol include ethyleneglycol, propanediol, 2,2-dimethyl-propanediol, 1,6-hexanediol, and1,12-dodecanediol.

A fifth exemplary dihydroxy chain extender is a dihydroxy compound ofFormula (E), which may be useful for high heat applications:

wherein R¹³ and R¹⁵ are each independently halogen or C₁-C₆ alkyl, R¹⁴is C₁-C₆ alkyl, or phenyl substituted with up to five halogens or C₁-C₆alkyl groups, and c is 0 to 4. In specific embodiments, R¹⁴ is a C₁-C₆alkyl or phenyl group; or each c is 0. Compounds of Formula (E) include3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one (PPPBP).

Another dihydroxy chain extender that might impart high Tgs to thepolycarbonate has adamantane units. Such compounds may have repetitiveunits of the following formula (F) for high heat applications:

wherein R₁ is halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₆-C₁₂ aryl, C₇-C₁₃aryl-substituted alkenyl, or C₁-C₆ fluoroalkyl; R₂ is halogen, C₁-C₁₂alkyl, C₁-C₁₂ alkoxy, C₆-C₁₂ aryl, C₇-C₁₃ aryl-substituted alkenyl, orC₁-C₁₂ fluoroalkyl; m is an integer of 0 to 4; and n is an integer of 0to 14.

Another dihydroxy compound that might impart high Tgs to thepolycarbonate is a fluorene-unit containing dihydroxy compoundrepresented by the following Formula (G):

wherein R₁ to R₄ are each independently hydrogen, C₁-C₉ hydrocarbon, orhalogen.

Another dihydroxy chain extender that could be used is an isosorbide. Amonomer unit derived from isosorbide may be an isorbide-bisphenol unitof Formula (H):

wherein R₁ is an isosorbide unit and R₂-R₉ are each independently ahydrogen, a halogen, a C₁-C₆ alkyl, a methoxy, an ethoxy, or an alkylester.

The R₁ isosorbide unit may be represented by Formula (H-a):

The isosorbide unit may be derived from one isosorbide, or be a mixtureof isomers of isosorbide. The stereochemistry of Formula (I) is notparticularly limited. These diols may be prepared by the dehydration ofthe corresponding hexitols. The isosorbide-bisphenol may have a pKa ofbetween 8 and 11.

While the compounds of Formulas (A)-(H) are diols, diacids may also beused as the dihydroxy chain extender. Some exemplary diacids includethose having the structures of one of Formulas (1)-(2):

where Y is hydroxyl, halogen, alkoxy, or aryloxy; and where n is 1 to20. It should be noted that Formula (1) encompasses adipic acid (n=4),sebacic acid (n=8), and dodecanedioic acid (n=10). Similarly, Formula(2) encompasses isophthalic acid and terephthalic acid. When diacids areused, the crosslinkable polycarbonate of the present disclosure may be apolyester-polycarbonate. The molar ratio of ester units to carbonateunits in the polyester-polycarbonate may be 1:99 to 99:1, specifically10:90 to 90:10, more specifically 25:75 to 75:25.

The reaction mixture used to form the cross-linkable polycarbonateresins of the present disclosure also includes a carbonate precursor.The carbonate precursor serves as a carbonyl source. In particular, thecarbonate precursor may be phosgene, or may be a diaryl carbonate.Exemplary diaryl carbonates include for example diphenyl carbonate(DPC), ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresylcarbonate, and dinaphthyl carbonate, and are used in melt polymerizationprocesses. In interfacial polymerization processes, phosgene andcarbonyl halides are usually selected as the carbonate precursor.

Particularly contemplated for use in the processes of the presentdisclosure are phosgene and diphenyl carbonate (DPC), which areillustrated below as Formulas (3) and (4), respectively:

When a monohydroxybenzophenone is used to form endcaps, the molar ratioof the benzophenone to the dihydroxy chain extender(s) can be from 1:2to 1:200 prior to UV exposure, including from about 1:10 to about 1:200or from about 1:20 to about 1:200. When a dihydroxybenzophenone is usedas a monomer, the molar ratio of the benzophenone to the dihydroxy chainextender(s) can be from 1:1 to 1:200 prior to UV exposure, includingfrom 1:2 to 1:200, or from about 1:99 to about 3:97, or from about 1:99to about 6:94, or from about 10:90 to about 25:75 or from about 1:3 toabout 1:200.

If desired, the reaction mixture can include branching agents thatcontain three, four, or even more functional groups. The functionalgroups can be, for example, hydroxyl groups or carboxylic acid groups.Generally speaking, these react in the same way as the dihydroxy chainextender. Branching agents with three hydroxyl groups include1,1,1-trimethoxyethane; 1,1,1-trimethoxymethane; 1,1,1-tris(hydroxyphenyl) ethane (THPE), and1,3,5-tris[2-(4-hydroxyphenyl)-propan-2-yl]benzene. Branching agentswith four hydroxyl groups include pentaerythritol and4-[2,6,6-tris(4-hydroxyphenyl)heptan-2-yl]phenol. In other embodiments,the branching agent can be an oligomer, made from epoxidized novolacmonomer, that permit the desired number of functional groups to beprovided.

Branching agents having three carboxylic acid groups includebenzenetricarboxylic acid, citric acid, and cyanuric chloride. Branchingagents having four carboxylic acid groups include benzenetetracarboxylicacid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylicdianhydride. The corresponding acyl halides and esters of such acids arealso contemplated. Oligomers containing glycidyl methacrylate monomerswith styrene or methacrylate monomers are also contemplated.

An end-capping agent is generally used to terminate any polymer chainsof the photoactive additive. The end-capping agent (i.e. chain stopper)can be a monohydroxy compound, a mono-acid compound, or a mono-estercompound. Exemplary endcapping agents include phenol, p-cumylphenol(PCP), resorcinol monobenzoate, p-tert-butylphenol, octylphenol,p-cyanophenol, and p-methoxyphenol. Unless modified with otheradjectives, the term “end-capping agent” is used herein to denote acompound that is not photoactive when exposed to light. For example, theend-capping agent does not contain a ketone group. The photoactiveadditive may comprise about 0.5 mole % to about 5.0 mole % endcap groupsderived from this non-photoactive end-capping agent. It is noted thatwhen the cross-linkable polycarbonate resin contains amonohydroxybenzophenone, the monohydroxybenzophenone acts as anend-capping agent. In that situation, a second non-photoactiveend-capping agent can also be used. The photoactive additive maycomprise about 0.5 mole % to about 5.0 mole % endcap groups derived fromeach end-capping agent, including about 1 mole % to about 3 mole %, orfrom about 1.7 mole % to about 2.5 mole %, or from about 2 mole % toabout 2.5 mole %, or from about 2.5 mole % to about 3.0 mole % endcapgroups derived from each end-capping agent.

The cross-linkable polycarbonate resins of the present disclosure can bean oligomer or a polymer. The oligomer has a weight average molecularweight (Mw) of less than 15,000, including 10,000 or less. The polymericpolycarbonates of the present disclosure have a Mw of 15,000 or higher.In particular embodiments, the Mw is between 17,000 and 80,000 Daltons,or between 17,000 and 35,000 Daltons. These molecular weights aremeasured prior to any UV exposure. The Mw may be varied as desired. Insome particular embodiments, the Mw of the photoactive additives isabout 5,000 or less.

One example of a photoactive additive is a cross-linkable polycarbonateresin shown in FIG. 1. Here, 4,4′-dihydroxybenzophenone is reacted withphosgene (carbonate precursor), bisphenol-A (dihydroxy chain extender),and p-cumylphenol (end-capping agent) to obtain the cross-linkablepolycarbonate resin. A copolymer is thus formed with a weight averagemolecular weight and a polydispersity index, and containing carbonatelinkages.

FIG. 2 illustrates the formation of a branched cross-linkablepolycarbonate. As illustrated here, 4,4′-dihydroxybenzophenone isreacted with phosgene (carbonate precursor), bisphenol-A (dihydroxychain extender), p-cumylphenol (end-capping agent), and a branchingagent (1,1,1-tris-hydroxyphenylethane (THPE)). A copolymer is thusformed.

FIG. 3 illustrates the formation of another cross-linkablepolycarbonate. Here, 4-hydroxybenzophenone is reacted with phosgene(carbonate precursor) and bisphenol-A (dihydroxy chain extender) toobtain the cross-linkable polycarbonate resin.

FIG. 4 illustrates the formation of a cross-linkable polycarbonate. Asshown here, 4-hydroxybenzophenone is reacted with phosgene (carbonateprecursor), bisphenol-A (dihydroxy chain extender), p-cumylphenol(end-capping agent), and a branching agent (THPE).

One crosslinking mechanism of the photoactive additives is believed tobe due to hydrogen abstraction by the ketone group from an alkyl groupthat acts as a hydrogen donor and subsequent coupling of the resultingradicals. This mechanism is illustrated in FIG. 5 with reference to abenzophenone (the photoactive moiety) and a bisphenol-A (BPA) monomer.Upon exposure to UV, the oxygen atom of the benzophenone abstracts ahydrogen atom from a methyl group on the BPA monomer and becomes ahydroxyl group. The methylene group then forms a covalent bond with thecarbon of the ketone group. Put another way, the ketone group of thebenzophenone could be considered to be a photoactive group. It should benoted that the presence of hydrogen is critical for this reaction tooccur. Other mechanisms may occur after the initial abstraction eventwith base resins containing unsaturated bonds or reactive side groups.

In some embodiments, the cross-linkable polycarbonate resin containsrepeating units derived from a dihydroxybenzophenone monomer (i.e. ofFormula (II)). The cross-linkable polycarbonate resin may comprise fromabout 0.5 mole % to about 50 mole % of repeating units derived from thedihydroxybenzophenone. In more particular embodiments, thecross-linkable polycarbonate resin comprises from about 1 mole % toabout 3 mole %, or from about 1 mole % to about 5 mole %, or from about1 mole % to about 6 mole %, or from about 5 mole % to about 20 mole %,or from about 10 mole % to about 20 mole %, or from about 0.5 mole % toabout 25 mole % of repeating units derived from thedihydroxybenzophenone.

In more specific embodiments, the photoactive cross-linkablepolycarbonate resin is a terpolymer formed from the reaction of adihydroxybenzophenone, a first dihydroxy chain extender, a seconddihydroxy chain extender, a carbonate precursor, and optionally one ormore end-capping agents. The terpolymer contains from about 0.5 mole %to 50 mole % of repeating units derived from the dihydroxybenzophenone,from about 50 mole % to 99.5 mole % of repeating units derived from thefirst dihydroxy chain extender, and from about 50 mole % to 99.5 mole %of repeating units derived from the second dihydroxy chain extender.Most desirably, the dihydroxybenzophenone is 4,4′-dihydroxybenzophenone(4,4′-DHBP). Usually, the first dihydroxy chain extender is bisphenol-A.In particular embodiments, the cross-linkable polycarbonate terpolymerdoes not have photoactive endcaps.

Specific examples of contemplated terpolymers include those including asmonomers (i) DHBP; (ii) bisphenol-A; and (iii) a third monomer selectedfrom the group consisting of sebacic acid, a polysiloxane monomer,DMBPC, or tetrabromobisphenol-A.

In other specific embodiments, the photoactive cross-linkablepolycarbonate resin is a copolymer formed from the reaction of adihydroxybenzophenone, a first dihydroxy chain extender, a carbonateprecursor, and optionally one or more end-capping agents. The copolymercontains from about 0.5 mole % to 50 mole % of repeating units derivedfrom the dihydroxybenzophenone, and from about 50 mole % to 99.5 mole %of repeating units derived from the first dihydroxy chain extender. Mostdesirably, the dihydroxybenzophenone is 4,4′-dihydroxybenzophenone. Inparticular embodiments, the cross-linkable polycarbonate copolymer doesnot have photoactive endcaps. Specific examples of contemplatedcopolymers include a copolymer having as monomers (i) 4,4′-DHBP and (ii)bisphenol-A.

In yet other embodiments, the photoactive additive is a cross-linkablepolycarbonate resin comprising endcap groups derived from amonohydroxybenzophenone monomer (i.e. of Formula (I)). Thecross-linkable polycarbonate resin may comprise about 0.5 mole % toabout 5 mole % endcap groups derived from the monohydroxybenzophenone,including from about 1 mole % to about 3 mole, or from about 1.7 mole %to about 2.5 mole %, or from about 2 mole % to about 2.5 mole %, or fromabout 2.5 mole % to about 3.0 mole %, or from about 3.5 mole % to about4.0 mole % endcap groups derived from the monohydroxybenzophenone. Mostdesirably, the monohydroxybenzophenone is 4-hydroxybenzophenone (4-HBP).

In some specific embodiments, the photoactive cross-linkablepolycarbonate resin is a homopolymer formed from the reaction of amonohydroxybenzophenone, a single dihydroxy chain extender, a carbonateprecursor, and optionally a non-photoactive end-capping agent. Thecopolymer contains from about 0.5 mole % to about 5 mole % endcap groupsderived from the monohydroxybenzophenone. An exemplary homopolymer is abisphenol-A homopolycarbonate with 4-HBP endcaps.

In more specific embodiments, the photoactive cross-linkablepolycarbonate resin is a copolymer formed from the reaction of amonohydroxybenzophenone, a first dihydroxy chain extender, a seconddihydroxy chain extender, a carbonate precursor, and optionally anon-photoactive end-capping agent. The copolymer contains from about 0.5mole % to 99.5 mole % of repeating units derived from the firstdihydroxy chain extender, about 0.5 mole % to 99.5 mole % of repeatingunits derived from the second dihydroxy chain extender, and about from0.5 mole % to about 5 mole % endcap groups derived from themonohydroxybenzophenone. An exemplary copolymer is one formed frombisphenol-A and sebacic acid with 4-HBP endcaps.

These polycarbonates, prior to cross-linking, can be provided asthermally stable high melt-flow polymers, and can thus be used tofabricate a variety of thin-walled articles (e.g., 3 millimeters (mm) orless). These articles are subsequently exposed to ultraviolet radiationto affect cross-linking. The cross-linked materials, in addition toflame resistance and chemical resistance, may retain or exhibit superiormechanical properties (e.g., impact resistance, ductility) as comparedto the polycarbonate resin prior to cross-linking.

The cross-linkable polycarbonates of the present disclosure may have aglass transition temperature (Tg) of greater than 120° C., 125° C., 130°C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C., 165° C., 170°C., 175° C., 180° C., 185° C., 190° C., 200° C., 210° C., 220° C., 230°C., 240° C., 250° C., 260° C., 270° C., 280° C., 290° C., or 300° C., asmeasured using a differential scanning calorimetry method. In certainembodiments, the polycarbonates have glass transition temperaturesranging from about 120° C. to about 230° C., about 140° C. to about 160°C., about 145° C. to about 155° C., about 148° C. to about 152° C., orabout 149° C. to about 151° C.

The cross-linkable polycarbonates of the present disclosure may have aweight average molecular weight (Mw) of 15,000 to about 80,000 Daltons[±1,000 Daltons], or of 15,000 to about 35,000 Daltons [±1,000 Daltons],or of about 20,000 to about 30,000 Daltons [±1,000 Daltons], or of17,000 to about 80,000 Daltons. Molecular weight determinations may beperformed using gel permeation chromatography (GPC), using across-linked styrene-divinylbenzene column and calibrated topolycarbonate references using a UV-VIS detector set at 264 nm. Samplesmay be prepared at a concentration of about 1 mg/ml, and eluted at aflow rate of about 1.0 ml/min.

The cross-linkable polycarbonates of the present disclosure may have apolydispersity index (PDI) of about 2.0 to about 5.0, about 2.0 to about3.0, or about 2.0 to about 2.5. The PDI is measured prior to any UVexposure.

The cross-linkable polycarbonates of the present disclosure may have amelt flow rate (MFR) of 1 to 45 grams/10 min, 6 to 15 grams/10 min, 6 to8 grams/10 min, 6 to 12 grams/10 min, 2 to 30 grams/10 min, 5 to 30grams/10 min, 8 to 12 grams/10 min, 8 to 10 grams/10 min, or 20 to 30grams/10 min, using the ASTM D1238-13 method, 1.2 kg load, 300° C.temperature, 360 second dwell.

The cross-linkable polycarbonates of the present disclosure may have abiocontent of 2 wt % to 90 wt %; 5 wt % to 25 wt %; 10 wt % to 30 wt %;15 wt % to 35 wt %; 20 wt % to 40 wt %; 25 wt % to 45 wt %; 30 wt % to50 wt %; 35 wt % to 55 wt %; 40 wt % to 60 wt %; 45 wt % to 65 wt %; 55wt % to 70% wt %; 60 wt % to 75 wt %; 50 wt % to 80 wt %; or 50 wt % to90 wt %. The biocontent may be measured according to ASTM D6866-10.

The cross-linkable polycarbonates of the present disclosure may have amodulus of elasticity of greater than or equal to (≥) 2200 megapascals(MPa), ≥2310 MPa, ≥2320 MPa, ≥2330 MPa, ≥2340 MPa, ≥2350 MPa, ≥2360 MPa,≥2370 MPa, ≥2380 MPa, ≥2390 MPa, ≥2400 MPa, ≥2420 MPa, ≥2440 MPa, ≥2460MPa, ≥2480 MPa, ≥2500 MPa, or ≥2520 MPa as measured by ASTM D790-10 at1.3 mm/min, 50 mm span.

In embodiments, the cross-linkable polycarbonates of the presentdisclosure may have a flexural modulus of 2,200 to 2,500 MPa, preferably2,250 to 2,450 MPa, more preferably 2,300 to 2,400 MPa. In otherembodiments, the cross-linkable polycarbonates of the present disclosuremay have a flexural modulus of 2,300 to 2,600 MPa, preferably 2,400 to2,600 MPa, more preferably 2,450 to 2,550 MPa. The flexural modulus isalso measured by ASTM D790-10.

The cross-linkable polycarbonates of the present disclosure may have atensile strength at break of greater than or equal to (≥) 60 megapascals(MPa), ≥61 MPa, ≥62 MPa, ≥63 MPa, ≥64 MPa, ≥65 MPa, ≥66 MPa, ≥67 MPa,≥68 MPa, ≥69 MPa, ≥70 MPa, ≥71 MPa, ≥72 MPa, ≥73 MPa, ≥74 MPa, or ≥75MPa as measured by ASTM D638-10 Type I at 50 mm/min.

The cross-linkable polycarbonates of the present disclosure may possessa ductility of greater than or equal to (≥) 60%, ≥65%, ≥70%, ≥75%, ≥80%,≥85%, ≥90%, ≥95%, or 100% in a notched izod test at −20° C., −15° C.,−10° C., 0° C., 5° C., 10° C., 15° C., 20° C., 23° C., 25° C., 30° C.,or 35° C. at a thickness of 3.2 mm according to ASTM D256-10.

The cross-linkable polycarbonates of the present disclosure may have anotched Izod impact strength (NII) of greater than or equal to (≥) 500J/m, ≥550 J/m, ≥600 J/m, ≥650 J/m, ≥700 J/m, ≥750 J/m, ≥800 J/m, ≥850J/m, ≥900 J/m, ≥950 J/m, or ≥1000 J/m, measured at 23° C. according toASTM D256-10.

The cross-linkable polycarbonates of the present disclosure may have aheat distortion temperature of greater than or equal to 110° C., 111°C., 112° C., 113° C., 114° C., 115° C., 116° C., 117° C., 118° C., 119°C., 120° C., 121° C., 122° C., 123° C., 124° C., 125° C., 126° C., 127°C., 128° C., 129° C., 130° C., 131° C., 132° C., 133° C., 134° C., 135°C., 136° C., 137° C., 138° C., 139° C., 140° C., 141° C., 142° C., 143°C., 144° C., 145° C., 146° C., 147° C., 148° C., 149° C., 150° C., 151°C., 152° C., 153° C., 154° C., 155° C., 156° C., 157° C., 158° C., 159°C., 160, 161° C., 162° C., 163° C., 164° C., 165° C., 166° C., 167° C.,168° C., 169° C., or 170° C., as measured according to ASTM D648-07 at1.82 MPa, with 3.2 mm thick unannealed mm bar.

The cross-linkable polycarbonates of the present disclosure may have apercent haze value of less than or equal to (≤) 10.0%, ≤8.0%, ≤6.0%,≤5.0%, ≤4.0%, ≤3.0%, ≤2.0%, ≤1.5%, ≤1.0%, or ≤0.5% as measured at acertain thickness according to ASTM D1003-13. The polycarbonate haze maybe measured at a 2.0, 2.2, 2.4, 2.54, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8,or a 4.0 millimeter thickness. The polycarbonate may be measured at a0.125 inch thickness.

The polycarbonate may have a light transmittance greater than or equalto (≥) 50%, ≥60%, ≥65%, ≥70%, ≥75%, ≥80%, ≥85%, ≥90%, ≥95%, ≥96%, ≥97%,≥98%, ≥99%, ≥99.1%, ≥99.2%, ≥99.3%, ≥99.4%, ≥99.5%, ≥99.6%, ≥99.7%,≥99.8%, or ≥99.9%, as measured at certain thicknesses according to ASTMD1003-13. The polycarbonate transparency may be measured at a 2.0, 2.2,2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, or a 4.0 millimeter thickness.

In certain embodiments, the cross-linkable polycarbonates of the presentdisclosure do not include soft block or soft aliphatic segments in thepolycarbonate chain. For example, the following aliphatic soft segmentsthat may be excluded from the cross-linkable polycarbonates of thepresent disclosure include aliphatic polyesters, aliphatic polyethers,aliphatic polythioeithers, aliphatic polyacetals, aliphaticpolycarbonates, C—C linked polymers and polysiloxanes. The soft segmentsof aliphatic polyesters, aliphatic polyethers, aliphaticpolythioeithers, aliphatic polyacetals, aliphatic polycarbonates may becharacterized as having Number Average MWs (Mns) of greater than 600.

Processes

An interfacial polycondensation polymerization process for bisphenol-A(BPA) based polycarbonates can be used to prepare the cross-linkablepolycarbonates of the present disclosure. Although the reactionconditions for interfacial polymerization can vary, an exemplary processgenerally involves dissolving or dispersing one or more dihydric phenolreactants (e.g. bisphenol-A) in water, adding the resulting mixture to awater-immiscible solvent medium, and contacting the reactants with acarbonate precursor (e.g. phosgene) in the presence of a catalyst (e.g.triethylamine, TEA) and an acid acceptor such as an alkali metalhydroxide.

Four different processes are disclosed herein for producing someembodiments of the photoactive additive which contain carbonatelinkages. Each process includes the following ingredients: one or moredihydroxy chain extenders, an end-capping agent, a carbonate precursor,a base, a tertiary amine catalyst, water, and a water-immiscible organicsolvent. It should be noted that more than one of each ingredient can beused to produce the crosslinkable polycarbonates. Some information oneach ingredient is first provided below.

A hydroxybenzophenone is present as the photoactive moiety, and can bepresent either as the end-capping agent (i.e. monohydroxybenzophenone)or as a diol (i.e. dihydroxybenzophenone). In the process descriptionsbelow, reference will be made to dihydroxy compounds, which should beconstrued as including the dihydroxy chain extender and adihydroxybenzophenone monomer. Reference will also be made to theend-capping agent, which should be construed as including amonohydroxybenzophenone.

The dihydroxy chain extender may have the structure of any one ofFormulas (A)-(H) or (1)-(2), and include monomers such as bisphenol-A.

Examples of end-capping agents (other than the monohydroxybenzophenone)include phenol, p-cumylphenol (PCP), p-tert-butylphenol, octylphenol,and p-cyanophenol.

The carbonate precursor may be, for example, a carbonyl halide such ascarbonyl dibromide or carbonyl dichloride (also known as phosgene), or ahaloformate such as a bishaloformate of a dihydric phenol (e.g., thebischloroformate of bisphenol-A, hydroquinone, or the like) or a glycol(e.g., the bishaloformate of ethylene glycol, neopentyl glycol,polyethylene glycol, or the like). Combinations comprising at least oneof the foregoing types of carbonate precursors can also be used. Incertain embodiments, the carbonate precursor is phosgene, a triphosgene,diacyl halide, dihaloformate, dicyanate, diester, diepoxy,diarylcarbonate, dianhydride, diacid chloride, or any combinationthereof. An interfacial polymerization reaction to form carbonatelinkages may use phosgene as a carbonate precursor, and is referred toas a phosgenation reaction. The compounds of Formulas (3) or (4) arecarbonate precursors.

The base is used for the regulation of the pH of the reaction mixture.In particular embodiments, the base is an alkali metal hydroxide, suchas sodium hydroxide (NaOH) or potassium hydroxide (KOH).

A tertiary amine catalyst is used for polymerization. Exemplary tertiaryamine catalysts that can be used are aliphatic tertiary amines such astriethylamine (TEA)), N-ethylpiperidine, 1,4-diazabicyclo[2.2.2]octane(DABCO), tributylamine, cycloaliphatic amines such asN,N-diethyl-cyclohexylamine and aromatic tertiary amines such asN,N-dimethylaniline.

Sometimes, a phase transfer catalyst is also used. Among the phasetransfer catalysts that can be used are catalysts of the formula(R³⁰)₄Q⁺X, wherein each R³⁰ is the same or different, and is a C₁-C₁₀alkyl group; Q is a nitrogen or phosphorus atom; and X is a halogenatom, C₁-C₈ alkoxy group, or C₆-C₁₈ aryloxy group. Exemplary phasetransfer catalysts include, for example, [CH₃(CH₂)₃]₄NX, [CH₃(CH₂)₃]₄PX,[CH₃(CH₂)₅]₄NX, [CH₃(CH₂)₆]₄NX, [CH₃(CH₂)₄]₄NX, CH₃[CH₃(CH₂)₃]₃NX, andCH₃[CH₃(CH₂)₂]₃NX, wherein X is Cl⁻, Br⁻, a C₁-C₈ alkoxy group or aC₆-C₁₈ aryloxy group, such as methyltributylammonium chloride.

The most commonly used water-immiscible solvents include methylenechloride, 1,2-dichloroethane, chlorobenzene, toluene, and the like.

In the first process, sometimes referred to as the “upfront” process,the diol(s), end-capping agent, catalyst, water, and water-immisciblesolvent are combined upfront in a vessel to form a reaction mixture. Thereaction mixture is then exposed to the carbonate precursor, for exampleby phosgenation, while the base is co-added to regulate the pH, toobtain the photoactive additive.

The pH of the reaction mixture is usually from about 8.5 to about 10,and can be maintained by using a basic solution (e.g. aqueous NaOH). Thereaction mixture is then charged with the carbonate precursor, which isusually phosgene. The carbonate precursor is added to the reactionmixture over a period of about 15 minutes to about 45 minutes. While thecarbonate precursor is being added, the pH is also maintained in therange of about 8.5 to about 10, again by addition of a basic solution asneeded. The cross-linkable polycarbonate is thus obtained, and is thenisolated from the reaction mixture.

In the second process, also known as the “solution addition” process,the diol(s), tertiary amine catalyst, water, and water-immisciblesolvent are combined in a vessel to form a reaction mixture. The totalcharge of the carbonate precursor is then added to this reaction mixturein the vessel over a total time period, while the base is co-added toregulate the pH. The carbonate precursor is first added to the reactionmixture along with the base to regulate the pH for a first time period.After the first time period ends, the end-capping agent is added in acontrolled manner to the reaction mixture, also referred to asprogrammed addition. The addition of the end-capping agent occurs for asecond time period after the first time period, rather than as a bolusat the beginning of the reaction (as in the upfront process). Thecarbonate precursor and the base are also added concurrently with theend-capping agent during the second time period. After the second timeperiod ends, the remainder of the carbonate precursor continuesuninterrupted for a third time period until the total charge is reached.The base is also co-added during the third time period to regulate thereaction pH. The pH of the reaction mixture is usually from about 8.5 toabout 10, and can be maintained by using a basic solution (e.g. aqueousNaOH, made from the base). The end-capping agent is not added duringeither the first time period or the third time period. The photoactiveadditive is thus obtained. The main difference between the first andsecond processes is in the addition of the end-capping agent over time.

In the second process, the carbonate precursor is added to the reactionmixture over a total time period, which may be for example from about 15minutes to about 45 minutes. The total time period is the durationneeded to add the total charge of the carbonate precursor (measuredeither by weight or by moles) to the reaction mixture. It iscontemplated that the carbonate precursor is added at a constant rateover the total time period. The carbonate precursor is first added tothe reaction mixture along with the base to regulate the pH for a firsttime period, ranging from about 2 minutes to about 20 minutes. Then,during a second time period, the end-capping agent is added to thereaction mixture concurrently with the carbonate precursor and the base.It is contemplated that the end-capping agent is added at a constantrate during this second time period, which can range from about 1 minuteto about 5 minutes. After the second time period ends, the remainingcarbonate precursor is charged to the reaction mixture for a third timeperiod, along with the base to regulate the reaction pH. Thecross-linkable polycarbonate is thus obtained, and is then isolated fromthe reaction mixture.

The total time period for the reaction is the sum of the first timeperiod, the second time period, and the third time period. In particularembodiments, the second time period in which the solution containing theend-capping agent is added to the reaction mixture begins at a pointbetween 10% to about 40% of the total time period. Put another way, thefirst time period is 10% of the total time period.

For example, if 2400 grams of phosgene were to be added to a reactionmixture at a rate of 80 g/min, and 500 ml of a PCP solution were to beadded to the reaction mixture at a rate of 500 ml/min after an initialcharge of 240 grams of phosgene, then the total time period would be 30minutes, the first time period would be three minutes, the second timeperiod would be one minute, and the third period would be 26 minutes.

The third process is also referred to as a bis-chloroformate orchlorofomate (BCF) process. Chloroformate oligomers are prepared byreacting a carbonate precursor, specifically phosgene, with the diol(s)in the absence of the tertiary amine catalyst, while the base isco-added to regulate the pH. The chloroformate oligomers can contain amixture of monochloroformates, bischloroformates, and bisphenolterminated oligomers. After the chloroformate oligomers are generated,the phosgene can optionally be allowed to substantially condense orhydrolyze, then the end-capping agent is added to the chloroformatemixture. The reaction is allowed to proceed, and the tertiary aminecatalyst is added to complete the reaction. The pH of the reactionmixture is usually from about 8.5 to about 10 prior to the addition ofthe phosgene. During the addition of the phosgene, the pH is maintainedbetween about 6 and about 8, by using a basic solution (e.g. aqueousNaOH).

The fourth process uses a tubular reactor. In the tubular reactor, theend-capping agent is pre-reacted with a carbonate precursor(specifically phosgene) to form chloroformates. The water-immisciblesolvent is used as a solvent in the tubular reactor. In a separatereactor, the diol(s), tertiary amine catalyst, water, andwater-immiscible solvent are combined to form a reaction mixture. Thechloroformates in the tubular reactor are then fed into the reactor overa first time period along with additional carbonate precursor tocomplete the reaction while the base is co-added to regulate the pH.During the addition of the chloroformates, the pH is maintained betweenabout 8.5 and about 10, by using a basic solution (e.g. aqueous NaOH).

The resulting cross-linkable polycarbonate formed by any of theseprocesses contains only a small amount of low-molecular-weightcomponents. This can be measured in two different ways: the level ofdiarylcarbonates (DAC) and the lows percentage can be measured.Diarylcarbonates are formed by the reaction of two end-capping agentswith phosgene, creating a small molecule. In embodiments, the resultingphotoactive additive contains less than 1000 ppm of diarylcarbonates.The lows percentage is the percentage by weight of oligomeric chainshaving a molecular weight of less than 1000. In embodiments, the lowspercentage is 2.0 wt % or less, including from about 1.0 wt % to 2.0 wt%. The DAC level and the lows percentage can be measured by highperformance liquid chromatography (HPLC) or gel permeationchromatography (GPC). Also of note is that the resulting photoactiveadditive does not contain any residual pyridine, because pyridine is notused in the manufacture of the photoactive additive.

Bromine Sources

The polymeric compositions of the present disclosure also include abromine source that provides bromine content to the polymericcomposition. The polymeric composition has from about 0.3 wt % to about15 wt % bromine content. In more particular embodiments, the polymericcomposition has from about 0.3 wt % to about 1 wt %, or from about 5 wt% to about 15 wt % of bromine content.

In various embodiments, the bromine source is a brominated polymer, abrominated oligomer, or a brominated flame retardant compound.

A brominated polymer or brominated oligomer may be used. One specificexample is a polycarbonate polymer/oligomer containing brominatedcarbonate units derived from2,2′,6,6′-tetrabromo-4,4′-isopropylidenediphenol (TBBPA) and carbonateunits derived from a dihydroxy aromatic compound such as bisphenol-A.The relative ratio of TBBPA to the dihydroxy aromatic compound used tomanufacture the TBBPA polymer/oligomer will depend in some embodimentson the amount of the TBBPA polymer/oligomer used and the amount ofbromine desired in the polymeric composition. In some embodiments, theTBBPA polymer/oligomer has 30 to 70 wt % of TBBPA and 30 to 70 wt % ofthe dihydroxy aromatic compound, specifically Bisphenol-A, orspecifically 45 to 55 wt % of TBBPA and 45 to 55 wt % of the dihydroxyaromatic compound, specifically bisphenol-A.

Combinations of different TBBPA polymers/oligomers can be used.Specifically, TBBPA polymers/oligomers can be used having phenolendcaps. Also, TBBPA polymers/oligomers can be used having2,4,6-tribromophenol endcaps.

Brominated polycarbonate oligomers are disclosed, for example, in U.S.Pat. No. 4,923,933, U.S. Pat. No. 4,170,711, and U.S. Pat. No.3,929,908. Examples of brominated aromatic dihydroxy compounds include2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane,bis(3,5-dibromo-4-hydroxyphenyl)menthanone, and2,2′,6,6′-tetramethyl-3,3′,5,5′-tetrabromo-4,4′-biphenol. Examples ofnon-brominated aromatic dihydroxy compounds for copolymerization withthe brominated aromatic dihydroxy compounds include Bisphenol-A,bis(4-hydroxyphenyl) methane, 2, 2-bis(4-hydroxy-3-methylphenyl)propane,4,4-bis(4-hydroxyphenyl)heptane, and(3,3′-dichloro-4,4′-dihydroxydiphenyl)methane. Combinations of two ormore different brominated and non-brominated aromatic dihydroxycompounds can be used. If a combination of aromatic dihydroxy compoundsis used, then the combinations can contain 25 to 55 mole percent of thebrominated aromatic dihydroxy compounds and 75 to 65 mole percent of anon-brominated dihydric phenol. Branched brominated polycarbonateoligomers can also be used, as can compositions of a linear brominatedpolycarbonate oligomer and a branched brominated polycarbonate oligomer.Combinations of different brominated copolycarbonate oligomers can beused. Various endcaps can be present, for example polycarbonates havingphenol endcaps or 2,4,6-tribromophenol endcaps can be used.

The brominated polymer/oligomer may contain brominated andnon-brominated monomers in a ratio such that the polymer/oligomercontains from about 5 wt % to about 30 wt % of bromine, based on thetotal weight of the polymer/oligomer.

One exemplary brominated polymer has a weight average molecular weightof about 23,660, a PDI of about 2.6, and a bromine content of 26%, andcan be made using interfacial polymerization methods.

Other types of brominated oligomers can be used, for example brominatedepoxy oligomers. Examples of brominated epoxy oligomers include thosederived from Bisphenol-A, hydrogenated Bisphenol-A, Bisphenol-F,Bisphenol-S, novolak epoxies, phenol novolac epoxies, cresol novolacepoxies, N-glycidyl epoxies, glyoxal epoxies dicyclopentadiene phenolicepoxies, silicone-modified epoxies, and epsilon-caprolactone modifiedepoxies. Combinations of different brominated epoxy oligomers can beused. Specifically, a tetrabromobisphenol-A epoxy be used, having2,4,6-tribromophenol endcaps. An epoxy equivalent weight of 200 to 3000can be used.

An exemplary brominated epoxy oligomer is F3100 from ICL IndustrialProducts, which has a molecular weight of about 15,000 and has a brominecontent of 53%.

The brominated polymers/oligomers can have an Mw from about 1,000 toabout 30,000 Daltons, as measured by gel permeation chromatography (GPC)using polycarbonate standards. In more specific embodiments, thebrominated polymers/oligomers can have an Mw from about 20,000 to about30,000 Daltons; or from about 1,000 to 18,000 Daltons; or from about2,000 to about 15,000 Daltons; or from about 3,000 to about 12,000Daltons.

Alternatively, the bromine source may be a brominated flame retardantcompounds. Such bromine-containing flame retardant compounds arewell-known in the art. Exemplary brominated flame retardants include apolybrominated diphenyl ether (PBDE); hexabromocyclododecane (HBCD);tetrabromobisphenol-A (TTBPA); bis(2,6-dibromophenyl)-methane;2,2-bis-(3-phenyl-4-bromophenyl)-ethane;2,2-bis-(3,5-dibromophenyl)-hexane; bis-(3-nitro-4-bromophenyl)-methane;2,2-bis-(3-bromo-4-hydroxyphenyl)-propane; 1,4-dibromobenzene;2,4′-dibromobiphenyl; and 1,2-bis(tetrabromophthalimido)ethane(commercially available as SAYTEX BT-93).

In other particular embodiments, the bromine source is the crosslinkablepolycarbonate resin itself. A brominated monomer, such astetrabromobisphenol-A (TTBPA), can be incorporated into thecrosslinkable polycarbonate resin.

Second Polymer Resin

The polymeric compositions/blends of the present disclosure can alsoinclude a polymeric base resin that is different from the photoactiveadditive, i.e. a second polymer resin. More specifically, the secondpolymer resin does not contain photoactive groups. In embodiments, theweight ratio of the cross-linkable polycarbonate resin to the polymericbase resin is from 1:99 to 99:1. When the additive contains amonohydroxybenzophenone, the weight ratio of the cross-linkablepolycarbonate resin to the polymeric base resin may be from about 50:50to about 95:5. When the additive contains a dihydroxybenzophenone, theweight ratio of the cross-linkable polycarbonate resin to the polymericbase resin may be from about 10:90 to about 85:15, or from about 25:75to about 50:50. The polymeric base resin has, in specific embodiments, aweight-average molecular weight of about 21,000 or greater, includingfrom about 21,000 to about 40,000.

The cross-linkable polycarbonate resins are suitable for blending withpolycarbonate homopolymers, polycarbonate copolymers, and polycarbonateblends. They are also suitable for blending with polyesters,polyarylates, polyestercarbonates, and polyetherimides.

The blends may comprise one or more distinct cross-linkablepolycarbonates, as described herein, and/or one or more cross-linkedpolycarbonate(s). The blends also comprise one or more additionalpolymers. The blends may comprise additional components, such as one ormore additives. In certain embodiments, a blend comprises across-linkable and/or cross-linked polycarbonate (Polymer A) and asecond polymer (Polymer B), and optionally one or more additives. Inanother embodiment, a blend comprises a combination of a cross-linkableand/or cross-linked polycarbonate (Polymer A); and a secondpolycarbonate (Polymer B), wherein the second polycarbonate is differentfrom the first polycarbonate.

The second polymer (Polymer B) may be any polymer different from thefirst polymer that is suitable for use in a blend composition. Incertain embodiments, the second polymer may be a polyester, apolyestercarbonate, a bisphenol-A homopolycarbonate, a polycarbonatecopolymer, a tetrabromobisphenol-A polycarbonate copolymer, apolysiloxane-co-bisphenol-A polycarbonate, a polyesteramide, apolyimide, a polyetherimide, a polyamideimide, a polyether, apolyethersulfone, a polyepoxide, a polylactide, a polylactic acid (PLA),or any combination thereof.

In certain embodiments, the polymeric base resin may be a vinyl polymer,a rubber-modified graft copolymer, an acrylic polymer,polyacrylonitrile, a polystyrene, a polyolefin, a polyester, apolyesteramide, a polysiloxane, a polyurethane, a polyamide, apolyamideimide, a polysulfone, a polyepoxide, a polyether, a polyimide,a polyetherimide, a polyphenylene ether, a polyphenylene sulfide, apolyether ketone, a polyether ether ketone, anacrylonitrile-butadiene-styrene (ABS) resin, anacrylic-styrene-acrylonitrile (ASA) resin, a polyethersulfone, apolyphenylsulfone, a poly(alkenylaromatic) polymer, a polybutadiene, apolyacetal, a polycarbonate, a polyphenylene ether, an ethylene-vinylacetate copolymer, a polyvinyl acetate, a liquid crystal polymer, anethylene-tetrafluoroethylene copolymer, an aromatic polyester, apolyvinyl fluoride, a polyvinylidene fluoride, a polyvinylidenechloride, tetrafluoroethylene, a polylactide, a polylactic acid (PLA), apolycarbonate-polyorganosiloxane block copolymer, or a copolymercomprising: (i) an aromatic ester, (ii) an estercarbonate, and (iii)carbonate repeat units. The blend composition may comprise additionalpolymers (e.g. a third, fourth, fifth, sixth, etc., polymer).

In certain embodiments, the polymeric base resin may be ahomopolycarbonate, a copolycarbonate, a polycarbonate-polysiloxanecopolymer, a polyester-polycarbonate, or any combination thereof. Incertain embodiments, the polymeric base resin is a p-cumyl phenol cappedpoly(isophthalate-terephthalate-resorcinol ester)-co-(bisphenol-Acarbonate) copolymer. In certain embodiments, the polymeric base resinis a polycarbonate-polysiloxane copolymer.

The p-cumyl phenol capped poly(isophthalate-terephthalate-resorcinolester)-co-(bisphenol-A carbonate) polymer or apolycarbonate-polysiloxane copolymer may have a polysiloxane contentfrom 0.4 wt % to 25 wt %. In one preferred embodiment, the polymericbase resin is a p-cumylphenol capped poly(19 mol %isophthalate-terephthalate-resorcinol ester)-co-(75 mol % bisphenol-Acarbonate)-co-(6 mol % resorcinol carbonate) copolymer (Mw=29,000Daltons). In another preferred embodiment, the polymeric base resin is ap-cumylphenol capped poly(10 wt % isophthalate-terephthalate-resorcinolester)-co-(87 wt % bisphenol-A carbonate)-co-(3 mol % resorcinolcarbonate) copolymer (Mw=29,000 Daltons).

In another preferred embodiment, the polymeric base resin is apolycarbonate polysiloxane copolymer. The polycarbonate-polysiloxanecopolymer may be a siloxane block co-polycarbonate comprising from about4 wt % siloxane (±10%) to about 25 wt % siloxane (±10%) and having asiloxane chain length of 10 to 200. In another preferred embodiment, thepolymeric base resin is a PC-siloxane copolymer with 20% siloxanesegments by weight.

In another preferred embodiment, the polymeric base resin is ap-cumylphenol capped poly(65 mol % BPA carbonate)-co-(35 mol %3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one (PPPBP) carbonate)copolymer (Mw=25,000 Daltons).

In another preferred embodiment, the polymeric base resin is apolyphosphonate polymer, a polyphosphonate copolymer, or apoly(polyphosphonate)-co-(BPA carbonate) copolymer.

In yet other embodiments, the polymer resin in the blend is selectedfrom the group consisting of a polycarbonate-polysiloxane copolymer; apolycarbonate resin having an aliphatic chain containing at least twocarbon atoms as a repeating unit in the polymer backbone; a copolyesterpolymer; a bisphenol-A homopolycarbonate; a polystyrene polymer; apoly(methyl methacrylate) polymer; a thermoplastic polyester; apolybutylene terephthalate polymer; a methylmethacrylate-butadiene-styrene copolymer; anacrylonitrile-butadiene-styrene copolymer; a dimethyl bisphenolcyclohexane-co-bisphenol-A copolymer; a polyetherimide; apolyethersulfone; and a copolycarbonate of bisphenol-A and1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane) (BPTMC).

In particular embodiments, the polymer resin in the blend is apolycarbonate-polysiloxane (PC—Si) copolymer. The polycarbonate units ofthe copolymer are derived from dihydroxy compounds having the structuresof any of the formulas described above, but particularly those of thechain extenders of Formulas (A) and (B). Some illustrative examples ofsuitable dihydroxy compounds include the following:1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl) ethane,2,2-bis(4-hydroxyphenyl) propane (hereinafter “bisphenol-A” or “BPA”),2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane,1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane,2,2-bis(4-hydroxy-1-methylphenyl) propane, and1,1-bis(4-hydroxy-t-butylphenyl) propane; resorcinol, substitutedresorcinol compounds such as 5-methyl resorcinol, 5-phenyl resorcinol,or 5-cumyl resorcinol; catechol; hydroquinone; and substitutedhydroquinones such as 2-methyl hydroquinone, 2-t-butyl hydroquinone,2-phenyl hydroquinone, 2-cumyl hydroquinone, or 2,3,5,6-tetramethylhydroquinone. Bisphenol-A is often part of the PC—Si copolymer.

The polymer resin (polymer B) in the blend can be a polycarbonate resinhaving an aliphatic chain containing at least two carbon atoms as arepeating unit in the polymer backbone. This resin can also beconsidered a “soft segment polycarbonate” (SSP) resin. Generallyspeaking, the SSP resin is a copolymer of an aromatic difunctionalcompound and an aliphatic difunctional compound. The aromaticdifunctional compound may have the structure of, for example, any ofFormulas (A)-(H), previously described as chain extenders above. Inspecific embodiments, the aromatic difunctional compound is a bisphenolof Formula (A). The aliphatic difunctional compound provides a longaliphatic chain in the backbone and may have the structure of Formula(D). Exemplary aliphatic diols that are useful in SSP resins includeadipic acid (n=4), sebacic acid (n=8), and dodecanedioic acid (n=10).The SSP resin can be formed, for example by the phosgenation ofbisphenol-A, sebacic acid, and p-cumyl phenol. The SSP resin containscarbonate linkages and ester linkages.

In this regard, it is believed that the cross-linking reaction rate ofthe cross-linkable polycarbonate resin and its yield are directlyrelated to the hydrogen-to-ketone ratio of the polymeric blend. Thus,the higher the hydrogen-to-ketone ratio of the blend, the higher therate of chain-extension reaction/crosslinking should be. Due to thepresence of the hydrogen-rich SSP resin with its aliphatic blocks, thehydrogen-to-ketone ratio is relatively high. As a result, thecrosslinking density and the resulting flame retardance and chemicalresistance should be very good for this blend. In addition, the SSPresin has very good flow properties. It is believed that the blendshould also have good flow, and should also retain its ductileproperties even after crosslinking.

The polymer resin (polymer B) in the blend can be a bisphenol-Ahomopolycarbonate. Such resins are available, for example as LEXAN fromSABIC Innovative Plastics.

The polymer resin (polymer B) in the blend can be a polystyrene polymer.Such polymers contain only polystyrene monomers. Thus, for example ABSand MBS should not be considered polystyrene polymers.

The polymer resin (polymer B) in the blend can be a thermoplasticpolyester. An exemplary polyester is PCTG, which is a copolymer derivedfrom the reaction of terephthalic acid, ethylene glycol, andcyclohexanedimethanol (CHDM). The PCTG copolymer can contain 40-90 mole% CHDM, with the terephthalic acid and the ethylene glycol making up theremaining 10-60 mole %.

The polymer resin (polymer B) in the blend can be a dimethyl bisphenolcyclohexane-co-bisphenol-A copolymer, i.e. a DMBPC-BPA copolymer. TheDMBPC is usually from 20 mole % to 90 mole % of the copolymer, including25 mole % to 60 mole %. The BPA is usually from 10 mole % to 80 mole %of the copolymer, including 40 mole % to 75 mole %. These resins havehigh scratch resistance.

Other Additives

Other conventional additives can also be added to the polymericcomposition (e.g. an impact modifier, UV stabilizer, colorant, flameretardant, heat stabilizer, plasticizer, lubricant, mold release agent,filler, reinforcing agent, antioxidant agent, antistatic agent, blowingagent, or radiation stabilizer).

In preferred embodiments, the blend compositions disclosed hereincomprise a flame-retardant, a flame retardant additive, and/or an impactmodifier. The flame-retardant may be potassium perfluorobutane sulfonate(Rimar salt), potassium diphenyl sulfone-3-sulfonate (KSS), or acombination thereof.

Various types of flame retardants can be utilized as additives. Thisincludes flame retardant salts such as alkali metal salts ofperfluorinated C₁-C₁₆ alkyl sulfonates such as potassium perfluorobutanesulfonate (Rimar salt), potassium perfluoroctane sulfonate,tetraethylammonium perfluorohexane sulfonate, potassium diphenylsulfonesulfonate (KSS), and the like, sodium benzene sulfonate, sodium toluenesulfonate (NATS) and the like. Rimar salt and KSS and NATS, alone or incombination with other flame retardants, are particularly useful in thecompositions disclosed herein. In certain embodiments, the flameretardant does not contain bromine or chlorine, i.e. is non-halogenated.Another useful class of flame retardant is the class of cyclic siloxaneshaving the general formula [(R)₂SiO]_(y) wherein R is a monovalenthydrocarbon or fluorinated hydrocarbon having from 1 to 18 carbon atomsand y is a number from 3 to 12. A particularly useful cyclic siloxane isoctaphenylcyclotetrasiloxane.

Exemplary heat stabilizer additives include, for example,organophosphites such as triphenyl phosphite,tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono- anddi-nonylphenyl)phosphite or the like; phosphonates such asdimethylbenzene phosphonate or the like; phosphates such as trimethylphosphate, or the like; or combinations thereof. Heat stabilizers aregenerally used in amounts of 0.0001 to 1 part by weight, based on 100parts by weight of the polymer component of the polymericblend/composition.

Mold release agent (MRA) will allow the material to be removed quicklyand effectively. Mold releases can reduce cycle times, defects, andbrowning of finished product. Exemplary MRAs include phthalic acidesters; di- or polyfunctional aromatic phosphates such as resorcinoltetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate ofhydroquinone and the bis(diphenyl) phosphate of bisphenol-A;pentaerythritol tetrastearate (PETS), and the like. Such materials aregenerally used in amounts of 0.001 to 1 part by weight, specifically0.01 to 0.75 part by weight, more specifically 0.1 to 0.5 part byweight, based on 100 parts by weight of the polymer component of thepolymeric blend/composition.

In particular embodiments, the polymeric blend/composition includes thecross-linkable polycarbonate resin, an optional polymeric base resin,and a flame retardant which is Rimar salt and which is present in anamount of about 0.05 wt % to about 0.085 wt %, based on the total weightof the composition; and a plaque comprising the polymeric compositionhas a transparency of 70 to 90% at a thickness of 3.2 mm, measuredaccording to ASTM D1003-13.

In other particular embodiments, the polymeric blend/compositionincludes the cross-linkable polycarbonate resin, an optional polymericbase resin, a flame retardant; a heat stabilizer, and a mold releaseagent.

The additives, when used, can improve various properties of the finalarticle. Increased chemical resistance may be found against 409 Glassand Surface Cleaner; Alcohol Prep Pad; CaviCide liquid/CaviWipes;CaviWipes; Cidex Plus liquid; Clorox Bleach; Clorox Wipes; Envirocideliquid; ForPro liquid; Gentle dish soap and water; Hydrogen PeroxideCleaner Disinfectant Wipes; Isopropyl Alcohol wipes; MadaCide-1 liquid;Mar-V-Cide liquid to dilute; Sani-Cloth Bleach Wipes; Sani-Cloth HBWipes; Sani-Cloth Plus Wipes; Sodium Hypochlorite liquid; SuperSani-Cloth Wipes; Viraguard liquid and Wipes; Virex 256; Windex Blue;Fuel C; Toluene; Heptane; Ethanol; Isopropanol; Windex; Engine oil;WD40; Transmission fluid; Break fluid; Glass wash; Diesel; Gasoline;Banana Boat Sunscreen (SPF 30); Sebum; Ivory Dish Soap; SC JohnsonFantastik Cleaner; French's Yellow Mustard; Coca-Cola; 70% IsopropylAlcohol; Extra Virgin Olive Oil; Vaseline Intensive Care Hand Lotion;Heinz Ketchup; Kraft Mayonnaise; Chlorox Formula 409 Cleaner; SC JohnsonWindex Cleaner with Ammonia; Acetone; Artificial Sweat; Fruits & PassionCucina Coriander & Olive Hand Cream; Loreal Studioline Megagel Hair Gel;Maybelline Lip Polish; Maybelline Expert Wear Blush—Beach Plum Rouge;Purell Hand Sanitizer; Hot coffee, black; iKlear; Chlorox Wipes;Squalene; Palmitic Acid; Oleic Acid; Palmitoleic Acid; Stearic Acid; andOlive Oil.

Articles

The compositions/blends can be molded into useful shaped articles by avariety of means such as injection molding, overmolding, co-injectionmolding, extrusion, multilayer extrusion, rotational molding, blowmolding and thermoforming to form articles. This includes thin-walledarticles, including highly transparent thin-walled articles. The formedarticles may be subsequently subjected to cross-linking conditions(e.g., UV-radiation) to affect cross-linking of the polycarbonates.Exemplary articles include a film, a sheet, a layer of a multilayerfilm, or a layer of a multilayer sheet.

Articles that may be formed from the compositions/blends include variouscomponents for cell phones and cell phone covers, components forcomputer housings (e.g. mouse covers), fibers, computer housings andbusiness machine housings and parts such as housings and parts formonitors, computer routers, copiers, desk top printers, largeoffice/industrial printers handheld electronic device housings such ascomputer or business machine housings, housings for hand-held devices,components for light fixtures or home or office appliances, humidifierhousings, thermostat control housings air conditioner drain pans,outdoor cabinets, telecom enclosures and infrastructure, Simple NetworkIntrusion Detection System (SNIDS) devices, network interface devices,smoke detectors, components and devices in plenum spaces, components formedical applications or devices such as medical scanners, X-rayequipment, and ultrasound devices, components for interior or exteriorcomponents of an automobile, lenses (auto and non-auto) such ascomponents for film applications, greenhouse components, sun roomcomponents, fire helmets, safety shields, safety goggles, glasses withimpact resistance, fendors, gas pumps, films for televisions, such asecofriendly films having no halogen content, solar applicationmaterials, glass lamination materials, fibers for glass-filled systems,hand held electronic device enclosures or parts (e.g. walkie-talkie,scanner, media/MP3/MP4 player, radio, GPS system, ebook, tablet),wearable electronic devices (e.g. smart watch, training/tracking device,activity/sleep monitoring system, wristband, or glasses), hand held toolenclosures or parts, smart phone enclosures or parts, turbine blades(e.g., wind turbines), and the like.

In certain embodiments, articles that may comprise the composition/blendinclude automotive bumpers, other automotive, construction andagricultural equipment exterior components, automobile mirror housings,an automobile grille, an automobile pillar, automobile wheel covers,automobile, construction and agricultural equipment instrument panelsand trim, construction and agricultural grilles, automobile glove boxes,automobile door hardware and other interior trim, automobileconstruction and agricultural equipment exterior lights, automobileparts within the engine compartment, plumbing equipment, valves andpumps, air conditioning heating and cooling parts, furnace and heat pumpparts, computer parts, electronics parts, projector parts, electronicdisplay parts, copier parts, scanner parts, electronic printer tonercartridges, hair driers, irons, coffee makers, toasters, washingmachines, microwaves, ovens, power tools, electric components, lightingparts, dental instruments and equipment, medical instruments, cookware,medical instrument trays, animal cages, fibers, laser welded medicaldevices, hand held electronic device enclosures or parts (e.g.walkie-talkie, scanner, media/MP3/MP4 player, radio, GPS system, ebook,tablet), wearable electronic devices (e.g. smart watch,training/tracking device, activity/sleep monitoring system, wristband,or glasses), hand held tool enclosures or parts, smart phone enclosuresor parts, and fiber optics.

In certain embodiments, articles that may comprise the composition/blendinclude automotive bumpers, other automotive exterior components,automobile mirror housings, an automobile grille, an automobile pillar,automobile wheel covers, automobile instrument panels and trim,automobile glove boxes, automobile door hardware and other interiortrim, external automobile trim parts, such as pillars, automobileexterior lights, automobile parts within the engine compartment, anagricultural tractor or device part, a construction equipment vehicle ordevice part, a construction or agricultural equipment grille, a marineor personal water craft part, an all-terrain vehicle or all-terrainvehicle part, plumbing equipment, valves and pumps, air conditioningheating and cooling parts, furnace and heat pump parts, computer parts,electronics parts, projector parts, electronic display parts, copierparts, scanner parts, electronic printer toner cartridges, hair driers,irons, coffee makers, toasters, washing machines, microwaves, ovens,power tools, electric components, electric enclosures, lighting parts,dental instruments, medical instruments, medical or dental lightingparts, an aircraft part, a train or rail part, a seating component,sidewalls, ceiling parts, cookware, medical instrument trays, animalcages, fibers, laser welded medical devices, fiber optics, lenses (autoand non-auto), cell phone parts, greenhouse components, sun roomcomponents, fire helmets, safety shields, safety glasses, gas pumpparts, hand held electronic device enclosures or parts (e.g.walkie-talkie, scanner, media/MP3/MP4 player, radio, GPS system, ebook,tablet), wearable electronic devices (e.g. smart watch,training/tracking device, activity/sleep monitoring system, wristband,or glasses), hand held tool enclosures or parts, smart phone enclosuresor parts, and turbine blades.

In certain embodiments, the article is one that requires or must includea material having a UL94 5VA rating performance. Articles that require aUL94 5VA rating include, but are not limited to, computer housings,computer housings and business machine housings and parts such ashousings and parts for monitors, computer routers, copiers, desk topprinters, large office/industrial printers, handheld electronic devicehousings such as computer or business machine housings, housings forhand-held devices, components for light fixtures including LED fixturesor home or office appliances, humidifier housings, thermostat controlhousings, air conditioner drain pans, outdoor cabinets, telecomenclosures and infrastructure, Simple Network Intrusion Detection System(SNIDS) devices, network interface devices, smoke detectors, componentsand devices in plenum spaces, components for medical applications ordevices such as medical scanners, X-ray equipment, and ultrasounddevices, electrical boxes and enclosures, and electrical connectors.

In certain embodiments, the article is one that requires hydrothermalstability, such as a wind turbine blade, a steam sterilizable medicaldevice, a food service tray, utensils and equipment.

In certain embodiments, the article is one that requires a combinationof transparency, flame resistance, and/or impact resistance. Forexample, in certain embodiments the article may be a safety shield,safety goggles, a gas/fuel pump housing, a display window or part, orthe like.

Ultraviolet Irradiation

After forming the article, the article can then be exposed toultraviolet (UV) light at an appropriate wavelength and dosage to bringabout the desired amount of crosslinking for the given application. TheUV exposure can be performed on one or more surfaces of the article.

The article should be exposed with a substantially uniform dose of UVlight. The exposure can be accomplished using standard methods known inthe art. For example, the UV light can come from any source of UV lightsuch as, but not limited to, those lamps powered by microwave, HIDlamps, and mercury vapor lamps. In some other embodiments, the articleis exposed by using natural sunlight. The exposure time will bedependent on the application and color of material. It can range from afew minutes to several days. Alternatively, the crosslinking can beaccomplished by using a UV-emitting light source such as a mercuryvapor, High-Intensity Discharge (HID), or various UV lamps. For example,commercial UV lamps are sold for UV curing from manufacturers such asHereaus Noblelight and Fusion UV. Non-limiting examples of UV-emittinglight bulbs include mercury bulbs (H bulbs), or metal halide dopedmercury bulbs (D bulbs, H+ bulbs, and V bulbs). Other combinations ofmetal halides to create a UV light source are also contemplated.Exemplary bulbs could also be produced by assembling the lamp out ofUV-absorbing materials and considered as a filtered UV source. A mercuryarc lamp is not used for irradiation. An H bulb has strong output in therange of 200 nm to 320 nm. The D bulb has strong output in the 320 nm to400 nm range. The V bulb has strong output in the 400 nm to 420 nmrange.

It may also be advantageous to use a UV light source where the harmfulwavelengths (those that cause polymer degradation or excessiveyellowing) are removed or not present. Equipment suppliers such asHeraeus Noblelight and Fusion UV provide lamps with various spectraldistributions. The light can also be filtered to remove harmful orunwanted wavelengths of light. This can be done with optical filtersthat are used to selectively transmit or reject a wavelength or range ofwavelengths. These filters are commercially available from a variety ofcompanies such as Edmund Optics or Praezisions Glas & Optik GmbH.Bandpass filters are designed to transmit a portion of the spectrum,while rejecting all other wavelengths. Longpass edge filters aredesigned to transmit wavelengths greater than the cut-on wavelength ofthe filter. Shortpass edge filters are used to transmit wavelengthsshorter than the cut-off wavelength of the filter. Various types ofmaterials, such as borosilicate glass, can be used as a long passfilter. Schott and/or Praezisions Glas & Optik GmbH for example have thefollowing long pass filters: WG225, WG280, WG295, WG305, WG320 whichhave cut-on wavelengths of ˜225, 280, 295, 305, and 320 nm,respectively. These filters can be used to screen out the harmful shortwavelengths while transmitting the appropriate wavelengths for thecrosslinking reaction.

In some embodiments, the UV radiation is filtered to provide exposure toUVA radiation with no detectable UVC radiation, as measured using an EITPowerPuck. The effective dosage can range from at least 1 Joule persquare centimeter (J/cm²) of UVA radiation up to about 60 J/cm² of UVAradiation. In more specific embodiments, the UV radiation is filtered toprovide an effective dosage at least 2 J/cm², or at least 3 J/cm², or atleast 12 J/cm², or at least 21 J/cm², or at least 36 J/cm² of UVAradiation, with no detectable UVC radiation, as measured using an EITPowerPuck. In particular embodiments, the polycarbonate fibers areexposed to a dosage of about 21 J/cm² to about 60 J/cm² of UVAradiation, or in more particular embodiments a dosage of about 21 J/cm²to about 36 J/cm² of UVA radiation.

The exposed article will have a cross-linked outer surface and an innersurface that is either lightly cross-linked or not cross-linked. Theouter surface can be cross-linked to such a degree that the outersurface is substantially insoluble in the common solvents for thestarting resins. The percentage of the insolubles (insoluble component)will be dependent on the part geometry and surface-to-volume ratio.

The following examples are provided to illustrate the polymericcompositions/blends, articles, processes, and properties of the presentdisclosure. The examples are merely illustrative and are not intended tolimit the disclosure to the materials, conditions, or process parametersset forth therein.

EXAMPLES

Molecular weight determinations were performed using gel permeationchromatography (GPC), using a cross-linked styrene-divinylbenzene columnand calibrated to polycarbonate references using a UV-VIS detector setat 264 nm. Samples were prepared at a concentration of about 1 mg/ml,and eluted at a flow rate of about 1.0 milliliter per minute (ml/min).Optionally, a refractive index (RI) detector can be used. The percentagechange in the molecular weight was calculated as the change divided bythe molecular weight before UV exposure.

Flammability testing was conducted using the standard UnderwritersLaboratory UL 94 test method (2 day or 7 day conditioning), except that20 bars rather than the usual 5 bars were tested. Specimens are to bepreconditioned either at room temperature for 48 hours or in anair-circulating oven for 168 hours at 70±1° C. and then cooled in adesiccator for at least 4 hours at room temperature, prior to testing.Once removed from the desiccator, specimens are tested within 30minutes.

Flammability tests were performed following the procedure ofUnderwriter's Laboratory Bulletin 94 entitled “Tests for Flammability ofPlastic Materials, UL94”. Several ratings can be applied based on therate of burning, time to extinguish, ability to resist dripping, andwhether or not drips are burning. According to this procedure, materialsmay be classified as HB, V0, V1, V2, 5V, 5VA and/or 5VB on the basis ofthe test results obtained for five samples. The criteria for theflammability classifications or “flame retardance” are described below.

V0: A specimen is supported in a vertical position and a flame isapplied to the bottom of the specimen. The flame is applied for tenseconds and then removed until flaming stops at which time the flame isreapplied for another ten seconds and then removed. Two sets of fivespecimens are tested. The two sets are conditioned under differentconditions.

To achieve a V0 rating, specimens must not burn with flaming combustionfor more than 10 seconds after either test flame application. Totalflaming combustion time must not exceed 50 seconds for each set of 5specimens. Specimens must not burn with flaming or glowing combustion upto the specimen holding clamp. Specimens must not drip flaming particlesthat ignite the cotton. No specimen can have glowing combustion remainfor longer than 30 seconds after removal of the test flame

5VA: Testing is done on both bar and plaque specimens. Procedure forBars: A bar specimen is supported in a vertical position and a flame isapplied to one of the lower corners of the specimen at a 20° angle. Theflame is applied for 5 seconds and is removed for 5 seconds. The flameapplication and removal is repeated five times. Procedure for Plaques:The procedure for plaques is the same as for bars except that the plaquespecimen is mounted horizontally and a flame is applied to the center ofthe lower surface of the plaque.

To achieve a 5VA rating, specimens must not have any flaming or glowingcombustion for more than 60 seconds after the five flame applications.Specimens must not drip flaming particles that ignite the cotton. Plaquespecimens must not exhibit burnthrough (a hole). It is noted that in theExamples and Tables below, the rows that state whether 5VA was “Pass” or“Fail” for a given thickness refer only to whether the plaque test waspassed, and should not be interpreted as stating that no combustionoccurred for more than 60 seconds and that there were no drips. Resultsfor both 2-day and 7-day conditioning are reported.

The data was analyzed by calculation of the average flame out time,standard deviation of the flame out time and the total number of drips.Statistical methods were used to convert the data to a probability thata specific formulation would achieve a first time V0 pass or “p(FTP)” inthe standard UL 94 testing of 5 bars. The probability of a first timepass on a first submission (pFTP) may be determined according to theformula:pFTP=(P _(t1>mbt,n=0) ×P _(t2>mbt,n=0) ×P _(total<=mtbt)×_(P drip,n=0))where P_(t1>mbt,n=0) is the probability that no first burn time exceedsa maximum burn time value, P_(t2>mbt,n=0) is the probability that nosecond burn time exceeds a maximum burn time value, P_(total<=mtbt) isthe probability that the sum of the burn times is less than or equal toa maximum total burn time value, and P_(drip,n=0) is the probabilitythat no specimen exhibits dripping during the flame test. First andsecond burn time refer to burn times after a first and secondapplication of the flame, respectively.

The probability that no first burn time exceeds a maximum burn timevalue, P_(t1>mbt,n=0), may be determined from the formula:P_(t1>mbt,n=0)=(1−P_(t1>mbt))⁵ where P_(t1>mbt) is the area under thelog normal distribution curve for t1>mbt, and where the exponent “5”relates to the number of bars tested. The probability that no secondburn time exceeds a maximum burn time value may be determined from theformula: P_(t2>mbt,n=0)=(1−P_(t2>mbt)) where P_(t2>mbt) is the areaunder the normal distribution curve for t2>mbt. As above, the mean andstandard deviation of the burn time data set are used to calculate thenormal distribution curve. For the UL-94 V-0 rating, the maximum burntime is 10 seconds. For a V-1 or V-2 rating the maximum burn time is 30seconds. The probability P_(drip, n=0) that no specimen exhibitsdripping during the flame test is an attribute function, estimated by:(1−P_(drip))⁵ where P_(drip)=(the number of bars that drip/the number ofbars tested).

The probability P_(total<=mtbt) that the sum of the burn times is lessthan or equal to a maximum total burn time value may be determined froma normal distribution curve of simulated 5-bar total burn times. Thedistribution may be generated from a Monte Carlo simulation of 1000 setsof five bars using the distribution for the burn time data determinedabove. Techniques for Monte Carlo simulation are well known in the art.A normal distribution curve for 5-bar total burn times may be generatedusing the mean and standard deviation of the simulated 1000 sets.Therefore, P_(total<=mtbt) may be determined from the area under a lognormal distribution curve of a set of 1000 Monte Carlo simulated 5-bartotal burn time for total<=maximum total burn time. For the UL94 V0rating, the maximum total burn time is 50 seconds. For a V1 rating, themaximum total burn time is 250 seconds.

Preferably p(FTP) values will be 1 or very close to 1 for highconfidence that a sample formulation would achieve a V0 rating in UL 94testing.

Samples were exposed to filtered UV light provided by a Loctite Zeta7411-S system, which used a 400 W metal halide arc lamp and behaved likea D-bulb electrodeless bulb in spectral output with a 280-nm cut-onwavelength filter. This was done because in prior experiments, filteredlight showed a lower change in YI for equivalent doses of UVA comparedto unfiltered UV light. The samples were exposed on both sides beneaththe UV lights for the equivalent UVA dosage of 36 J/cm² per side. The UVenergy (per pass or dose) for the Loctite system is provided below inTable A, and was measured using an EIT PowerPuck. The dose was measuredas the energy from 320-390 nm (UVA), 280-320 nm (UVB), 250-260 nm (UVC)and 395-445 nm (UVV). The dose was calculated in J/cm².

TABLE A Loctite (filtered light). Loctite Dose UVA UVB UVC UVV FilteredJ/cm² J/cm² J/cm² J/cm² 320 sec exposure 12.0 2.4 0 7.3 960 sec exposure36.0 7.2 0 21.9 1600 sec exposure  60.2 12.1 0 36.6

The MFR for each sample was calculated using the ASTM D1238-13 method,1.2 kg load, 300° C. temperature, 360 second or 1080 second dwell.

The Yellowness Index was measured before and/or after UV exposure usingan X-Rite Color i7 benchtop spectrophotometer in the transmission modeusing CIELAB color equation, an observer angle of 2 degrees, andilluminant C as the light source. YI was measured following ASTM E313-73(D1925).

Izod impact strength was measured at 23° C. according to ASTM D256-10,and is reported in J/m.

The various examples may contain the components shown in Table B.

TABLE B Trade name, Component Description Source HF-PC High-flowbisphenol-A homopolymer having Mw ~22,000 LF-PC Low-flow bisphenol-Ahomopolymer having Mw ~31,000 Bromo-PC tetrabromobisphenol-A/BPAcopolymer (TBBPA- BPA) containing 26.5 wt % bromine XPC-A Bisphenol-Ahomopolymer with 3.45 mole % of 4- hydroxybenzophenone endcaps XPC-BCopolymer of bisphenol-A and 10 mole % 4,4′- dihydroxybenzophenone(4,4′-DHBP) XPC-C Terpolymer containing bisphenol-A, 1 mole %tetrabromobisphenol-A, 10 mole % 4,4′-DHBP XPC-D Terpolymer containingbisphenol-A, 2 mole % tetrabromobisphenol-A, 20 mole % 4,4′-DHBP XPC-ETerpolymer containing bisphenol-A, 26 mole % tetrabromobisphenol-A, 10mole % 4,4′-DHBP XPC-F Terpolymer containing bisphenol-A, 26 mole %tetrabromobisphenol-A, 20 mole % 4,4′-DHBP DACRSBPApolysiloxane-Isophthalic acid-terephthalic acid- resorcinol-bisphenol-Acopolyestercarbonate copolymer; with an ester content of ~83 mol %, asiloxane content ~1 wt % (average siloxane chain length about 10),interfacial polymerization, Mw ~22,500 to 26,500 g/mol, para-cumylphenol end- capped PC-Si polysiloxane-polycarbonate block copolymer withabout 6 wt % of siloxane residues derived from polydimethylsiloxane and80 wt % of bisphenol-A, endcapped with p-cumylphenol, siloxane chainlength of about 40-60, and Mw of ~23,000 Phosphite Tris(2,4-di-tert-butylphenyl) phosphite Irgaphos 168 Rimar Salt Potassiumperfluorobutanesulfonate Lanxess Cyclic octaphenylcyclotetrasiloxanesiloxane TSAN Polytetrafluoroethylene encapsulated in styreneacrylonitrile copolymer, anti-drip agent KSS Potassiumdiphenylsulphon-3-sulphonate Arichem LLC PETS Pentaerythritoltetrastearate, >90% esterified, mold release agent UV36382,2′-(1,4-Phenylene)bis[4H-3,1-benzoxazin-4-one], Cyasorb UV- CAS#18600-59-4 3638, Cytec PEPQ Tetrakis(2,4-di-tert-butylphenyl)-4,4′- CibaSpecialty biphenylenediphosphonite Chemicals

Examples 1-7

Five batches of cross-linkable polycarbonate resin were made usingsolution program addition to obtain a crosslinkable bisphenol-Ahomopolycarbonate containing 3.45 mole % of 4-hydroxybenzophenoneendcaps (XPC-A). The resins had a weight average molecular weight of21,500 Daltons, measured using GPC with a UV detector. The batches hadan average polydispersity index of 3.8. The five batches were blendedand used to extrude the formulations of Table 1 (units in parts byweight).

Measurements were taken for melt flow rate. Each formulation was thenmolded into 20 flame bars of 1.2 millimeter thickness using injectionmolding. Each flame bar was then exposed to 36 J/cm² of UVA light oneach side using the Loctite Zeta 7411-S system. The samples then sat inthe dark for 48 hours before submission for UL V0 testing. UL V0 testingwas done following standard UL conditioning of 48 hours at 23° C. and at50% relative humidity. All of these results are shown in Table 1.

TABLE 1 Ingredient Ex-1 Ex-2 Ex-3 Ex-4 Ex-5 Ex-6 Ex-7 XPC-A 75 75 75 7575 75 75 LF-PC 25 25 25 25 25 25 25 Bromo-PC 1.25 Phosphite 0.06 0.060.06 0.06 0.06 0.06 0.06 Rimar Salt 0.08 0.08 0.08 0.08 Cyclic siloxane0.10 0.10 0.10 KSS 0.30 0.30 0.30 0.30 0.30 MFR (360 sec dwell) 9.539.83 9.54 9.69 9.56 9.57 9.84 p(FTP) for V0 @ 48 hr 0.4373 0.1389 0.09070.2331 0.2122 0.2323 0.9952 Flaming Drips @ 48 hr 1 0 0 0 0 0 0

Examples Ex-1 through Ex-6 did not include a brominated flame retardant.The best p(FTP) obtained was 0.4373 in Ex-1. However, this probabilitycould be increased to over 99% (0.9952) with the addition of abrominated polycarbonate flame retardant. Because none of the samplesshowed dripping behavior, the p(FTP) was clearly being driven by theflame out time, which is affected by the presence of the bromine.

Examples 8-15

Cross-linkable polycarbonate resin was made using solution programaddition to obtain a crosslinkable polycarbonate containing 10 mole %4,4′-dihydroxybenzophenone (XPC-B). The resins had a weight averagemolecular weight of 26,000 Daltons, measured using GPC with a UVdetector. The batches were used to make the formulations of Table 2 andTable 3 (units in parts by weight).

The different formulations were tested for melt flow rate (MFR), gelthickness, Izod impact, yellowness index, and haze. For Izod impact,yellowness index, and haze, measurements were taken both before andafter ultraviolet irradiation.

Each formulation was then molded into flame bars of varying thicknessusing injection molding. Each flame bar was then exposed to 36 J/cm² ofUVA light on each side using the Loctite Zeta 7411-S system. The samplesthen sat in the dark for 48 hours before submission for UL V0 testing.UL V0 testing was done following standard UL conditioning of 48 hours at° C. and at 50% relative humidity, and conditioning of 168 hours at 70°C. in a hot air oven. Chemical resistance testing was also performed.All of these results are shown in Table 2 and Table 3.

TABLE 2 Components Ex-8 Ex-9 Ex-10 Ex-11 XPC-B 25.00 25.00 25.00 25.00LF-PC 75.00 75.00 75.00 75.00 Bromo-PC Phosphite 0.06 0.06 0.06 0.06Rimar Salt 0.08 0.08 Cyclic Siloxane 0.10 0.10 KSS 0.30 0.30 MFR (360 s)7.8 7.69 7.5 7.56 MFR (1080 s) 7.54 8.02 7.48 7.52 Gel Thickness 60.5429.37 14.36 18.05 Izod Impact (Before/After UV) 883 858 YI unexposedpart 3.21 3.11 3.56 3.69 YI exposed part 18.97 20.85 17.16 17.34 DeltaYI 15.8 17.7 13.6 13.6 Haze unexposed part 0.47 0.43 1.20 1.25 Hazeexposed part 0.52 0.48 1.41 1.59 Delta Haze 0.1 0.0 0.2 0.3 FlamePerformance (UV exposure) p(FTP) for V0 @ 1.0 mm (48 hr) 0.36 0.93flaming drips 0 0 p(FTP) for V0 @ 1.2 mm (48 hr/ 0.43 0.39 0.70 0.660.66 0.41 0.49 0.09 168 hr) flaming drips 0 0 0 0 0 0 0 0 p(FTP) for V0@ 1.5 mm (48 hr) 0.76 0.67 flaming drips 0 0 Chemical Resistance(Elongation @ Break) As molded bar 119.5 Acetone @ 0.5% strain No UV10.6 Exposed to UV 99.6 Acetone @ 1% strain No UV Fail Exposed to UV88.4

TABLE 3 Components Ex-12 Ex-13 Ex-14 Ex-15 XPC-B 25.00 25.00 25.00 25.00LF-PC 75.00 75.00 75.00 75.00 Bromo-PC 1.25 1.25 Phosphite 0.06 0.060.06 0.06 Rimar Salt 0.08 0.08 Cyclic Siloxane 0.10 KSS 0.30 0.30 0.30MFR (360 s) 7.62 7.52 7.76 7.41 MFR (1080 s) 7.68 7.62 7.54 7.96 GelThickness 36.82 24.80 15.42 18.15 Izod Impact (Before/After UV) 872 866YI unexposed part 3.63 3.39 3.42 3.42 YI exposed part 16.35 18.50 16.0720.88 Delta YI 12.7 15.1 12.6 17.5 Haze unexposed part 9.16 7.34 1.280.62 Haze exposed part 7.92 6.38 1.81 0.77 Delta Haze −1.2 −1.0 0.5 0.1Flame Performance (UV exposure) p(FTP) for V0 @ 1.0 mm (48 hr) 0.99580.9944 flaming drips 0 0 p(FTP) for V0 @ 1.2 mm (48 hr/ 0.70 0.31 0.340.30 0.9925 0.996 0 0 168 hr) flaming drips 0 0 0 0 0 0 2/10 0/5 p(FTP)for V0 @ 1.5 mm (48 hr) 0.9182 0.9975 flaming drips 0 0 ChemicalResistance (Elongation @ Break) As molded bar 114.7 Acetone @ 0.5%strain No UV 2.7 Exposed to UV 105.7 Acetone @ 1% strain No UV FailExposed to UV 102.1

Examples Ex-8 through Ex-13 did not include a brominated flameretardant. The best p(FTP) obtained was 0.70 in Ex-9. However, thisprobability could be increased to over 99% (0.9952) with the addition ofa brominated polycarbonate flame retardant, as seen in Ex-14. Comparingthe non-brominated Ex-8 to brominated Ex-14, Ex-14 also had betterchemical resistance after exposure to UV.

Some combinations of flame retardants result in significant hazing. Forexample, Ex-12 and Ex-13 exhibit significant hazing when KSS and Rimarsalt are combined. However, both brominated examples, Ex-14 and Ex-15,exhibit minimal hazing. Comparing Ex-14 to Ex-15, the presence of KSSwas needed to pass the flame retardance tests due to the low amount ofbromine.

Examples 16-22

(XPC-C) Preparation of Cross-linkable Polycarbonate from Bisphenol-A,TBBPA (1 wt % Bromine), and 4,4′-Dihydroxybenzophenone (10 mole %)

A solution of p-cumylphenol (173 grams, 0.81 moles, 4.0 mole %) wasprepared in 500 mL of dichloromethane. The p-cumylphenol (PCP) solutionwas placed in an addition pot connected to the reactor via a dosingpump.

To the formulation tank was added dichloromethane (13 L), DI water (10L), bisphenol-A (3975 grams, 17.4 moles), tetrabromobisphenol-A (100grams, 0.2 moles, 1.1 wt % bromine), 4,4′-DHBP (425 grams, 2.0 moles,10.1 mole %) triethylamine (36 grams, 0.35 moles) and sodium gluconate(10 grams, iron scavenger). The mixture was stirred for 5 minutes, thentransferred to the 70 L batch reactor which was equipped with anoverhead condenser, circulation loop, pH probe and various materialaddition nozzles. The formulation tank was rinsed with dichloromethane(5 L) which was transferred to the batch reactor. The reactor agitatorwas started and the circulation flow was set at 80 L/min. Phosgene vaporflow to the reactor was initiated (80 g/min flow rate) by the DCS and aninitial amount (250 grams, 2.5 moles) was added. The pH of the reactionwas maintained at a target of 10.0 by DCS-controlled addition of 33%aqueous NaOH.

After addition of the initial amount of phosgene, the PCP solution wasadded to the reactor at 500 mL/min flow rate by DCS control whilephosgene flow to the reactor continued. Phosgene addition continueduntil the total set point was reached (2500 grams, 25.3 moles). Aftercompletion of the phosgene addition, a sample of the reactor wasobtained and verified to be free of un-reacted BPA and free ofchloroformate. Mw of a reaction sample was determined by GPC using a UVdetector (Mw=23605, PDI=2.5). An additional charge of phosgene was added(200 grams, 2.0 mole) to the reactor. The reactor was purged withnitrogen then the batch was transferred to the centrifuge feed tank.

To the batch in the centrifuge feed tank was added dilutiondichloromethane (8 L) then the mixture was purified using a train ofliquid-liquid centrifuges. Centrifuge one separated the brine phase.Centrifuge two removed the triethylamine catalyst by extracting theresin solution with aqueous hydrochloric acid (pH 1). Centrifuges threethrough eight removed residual ions by extracting the resin solutionwith DI water. A sample of the resin solution was tested and verifiedless than 5 ppm each of ionic chloride and residual triethylamine.

The resin solution was transferred to the precipitation feed tank. Theresin was isolated as a white powder by steam precipitation followed bydrying in a cone shaped vessel using heated nitrogen (210 F). Powderyield 2903 grams. Mw=23350 PDI=2.6.

(XPC-D) Preparation of Cross-Linkable Polycarbonate from Bisphenol-A,TBBPA (2 wt % Bromine), and 4,4′-Dihydroxybenzophenone (20 mole %)

The XPC-D polymer was prepared in the same manner as the XPC-C polymer,but with the following differences. First, the p-cumylphenol solutionwas (172 grams, 0.81 moles, 4.0 mole %) in 500 mL of dichloromethane.Second, to the formulation tank was added dichloromethane (13 L), DIwater (10 L), bisphenol-A (3475 grams, 15.2 moles),tetrabromobisphenol-A (185 grams, 0.34 moles, 2.1 wt % bromine),4,4′-DHBP (840 grams, 3.9 moles, 20.1 mole %) triethylamine (55 grams,0.54 moles) and sodium gluconate (10 grams, iron scavenger). Next, theMw of the reaction sample was Mw=23994, PDI=2.2. Last, the final powderyield was 2858 grams. Mw=23738 PDI=2.3.

(XPC-E) Preparation of Cross-Linkable Polycarbonate from Bisphenol-A,TBBPA (26 wt % Bromine), and 4,4′-Dihydroxybenzophenone (10 mole %)

The XPC-E polymer was prepared in the same manner as the XPC-C polymer,but with the following differences. First, the p-cumylphenol solutionwas (114 grams, 0.54 moles, 3.7 mole %) in 500 mL of dichloromethane.Second, to the formulation tank was added dichloromethane (13 L), DIwater (10 L), bisphenol-A (1925 grams, 8.4 moles), tetrabromobisphenol-A(2265 grams, 4.2 moles, 26.7 wt % bromine), 4,4′-DHBP (310 grams, 1.4moles, 10.3 mole %) triethylamine (95 grams, 0.94 moles) and sodiumgluconate (10 grams, iron scavenger). Next, the Mw of the reactionsample was Mw=24184, PDI=2.6. Last, the final powder yield was 2676grams. Mw=23613 PDI=2.7.

(XPC-F) Preparation of Cross-Linkable Polycarbonate from Bisphenol-A,TBBPA (26 wt % Bromine), and 4,4′-Dihydroxybenzophenone (20 mole %)

The XPC-F polymer was prepared in the same manner as the XPC-C polymer,but with the following differences. First, the p-cumylphenol solutionwas (114 grams, 0.81 moles, 3.6 mole %) in 500 mL of dichloromethane.Second, to the formulation tank was added dichloromethane (13 L), DIwater (10 L), bisphenol-A (1660 grams, 7.3 moles), tetrabromobisphenol-A(2225 grams, 4.1 moles, 26.2 wt % bromine), 4,4′-DHBP (615 grams, 2.9moles, 20.2 mole %) triethylamine (95 grams, 0.94 moles) and sodiumgluconate (10 grams, iron scavenger). Next, the Mw of the reactionsample was Mw=23835, PDI=2.6. Last, the final powder yield was 2087grams. Mw=22956 PDI=2.6.

Next, various compositions were made from these crosslinkableterpolymers having varying amounts of bromine and benzophenone. Theywere then compared to compositions that did not include benzophenone.

FAA testing was done according to FAR 25.853, Appendix F, Part I(a)(i),60 second vertical burn test standard. In the test, a testing specimenof 3 inches×12 inches is vertically mounted on a sample holder. A flameis then applied to the edge of the bottom of the tested specimen for 60seconds and then removed. The flammability requirements are as follows.Average burn length should be less than 6 inches; average flame timeafter removal of a flame should be less than 15 seconds; drippings maynot continue to burn more than 3 seconds. The average flame time(burning time) was reported.

Heat release testing was performed on 15.2×15.2 cm plaques 1.5 mm thickusing the Ohio State University (OSU) rate-of-heat release apparatus, inaccordance with the method shown in FAR 25.853 (d), and in Appendix F,section IV (FAR F25.4). Total heat release was measured at thetwo-minute mark in kW-min/m² (kilowatt minutes per square meter). Peakheat release was measured as kW/m² (kilowatts per square meter). Theheat release test method is also described in the “Aircraft MaterialsFire Test Handbook” DOT/FAA/AR-00/12, Chapter 5 “Heat Release Test forCabin Materials.”

Smoke density testing (ASTM E-662-83, ASTM F-814-83, Airbus ABD0031,Boeing BSS 7239) was performed on 7.5×7.5 cm plaques of 1.5 mm thicknessaccording to the method shown in FAR 25.853 (d), and in Appendix F,section V (FAR F25.5). Smoke density was measured under flaming mode.The max level (DsMax) was reported.

The results are shown in Table 4 and Table 5 (units in parts by weight).Flame performance is marked “F” for fail, and “P” for pass.

TABLE 4 Ingredient CE-1 Ex-16 Ex-17 CE-2 Ex-18 Ex-19 XPC-C (1% Br) 32.3813.04 XPC-D (2% Br) 16.19 6.52 XPC-B 11.96 11.96 LF-PC 92.86 66.89 83.0878.77 74.27 80.79 Bromo-PC (26% Br) 1.22 0.49 HF-PC 4.89 19.69 Phosphite0.09 0.09 0.09 0.09 0.09 0.09 TSAN 0.31 0.32 KSS 0.29 0.29 0.29 0.300.30 0.30 PETS 0.34 0.34 0.34 0.34 0.34 0.34 Total bromine (%) 0.32 0.320.32 0.13 0.13 0.13 MFR (360 s) 7.12 8.77 6.99 9.54 8.01 7.95 MFR (1080s) 7.98 8.82 7.45 9.15 8.09 7.71 YI unexposed part 11.22 2.66 1.94 YIexposed part 14.02 11.47 10.25 Delta YI 2.8 8.8 8.3 Haze unexposed part63.15 4.09 3.09 Haze exposed part 65.95 3.72 2.06 Delta Haze 2.8 −0.4−1.0 UL Flame Performance (UV exposure) p(FTP) for V0 @ 1.1 mm (48 hr/0.995/1.000 0.977/0.998 0.999/1.000 1.000/1.000 0.960/0.969 0.994/0.973168 hr) flaming drips 0/0 0/0 0/0 0/0 0/0 0/0 p(FTP) for V0 @ 1.5 mm (48hr/ 1.000/1.000 0.990/1.000 0.989/1.000 1.000/1.000 0.999/0.9800.978/0.999 168 hr) flaming drips 0/0 0/0 0/0 0/0 0/0 0/0 p(FTP) for V0@ 3.0 mm (48 hr/ 1.000/1.000 0.993/1.000 1.000/1.000 168 hr) flamingdrips 0/0 0/0 0/0 5VA @ 1.5 mm (48 hr/168 hr) F/F P/P P/P 5VA @ 3.0 mm(48 hr/168 hr) P/P P/P P/P

TABLE 5 Ingredient CE-3 Ex-20 CE-4 Ex-21 CE-5 Ex-22 XPC-C (1% Br) XPC-D(2% Br) XPC-E (26% Br) 24.99 24.91 XPC-F (26% Br) 11.99 XPC-B LF-PC74.97 74.97 Bromo-PC (26% Br) 24.99 39.86 14.95 11.99 HF-PC 9.96 9.96DACRSBPA 87.95 87.95 PC-Si 49.82 49.82 Phosphite 0.04 0.04 0.06 0.06UV3638 0.30 0.30 PEPQ 0.06 0.06 Total bromine (%) 6.50 6.50 10.36 10.363.12 3.12 MFR (360 s) 8.01 8.59 4.51 4.71 MFR (1080 s) 10.3 10.9 6.16.68 YI unexposed part 5.43 11.03 32.41 15.48 YI exposed part 10.2823.95 36.24 22.03 Delta YI 4.9 12.9 3.8 6.5 Haze unexposed 4.63 16.9026.50 4.28 part Haze exposed part 3.715 17.00 23.80 3.88 Delta Haze −0.90.1 −2.7 −0.4 Non-UL Flame Performance (UV exposure) FAA 60 sec 0 0 0 0(Time to drip) FAA 60 sec (P/F) Pass Pass Pass Pass OSU (Total/Peak)35/50 46/56 30/41 29/39 OSU (P/F) Pass Pass Pass Pass Smoke 92 40 27 32

The data supported the following conclusions. First, comparing CE-1/CE-2with E16-E19, TSAN could be removed and the compositions could stillretain V0 performance at thicknesses as low as 1.1 mm. Next, the removalof TSAN also turned the product from an opaque product to a transparentproduct, as seen in the reduction in YI and haze. The 5VA plaqueperformance was improved in E16/E17 compared to the TSAN formulation ofCE-1, maintaining a passing result at 1.5 mm thickness. Using thebrominated polycarbonate (Bromo-PC) did not negatively impact any flamecharacteristics. Finally, comparing CE-4 to E21, smoke levels were cutin half when crosslinkable polycarbonate was present.

Set forth below are some embodiments of the compositions disclosedherein.

Embodiment 1

A polymeric composition, comprising: a cross-linkable polycarbonateresin containing a photoactive group derived from a benzophenone; and abromine source present in an amount such that the polymeric compositioncontains from about 0.3 wt % to about 15 wt % bromine.

Embodiment 2

The composition of Embodiment 1, wherein the bromine source is thecross-linkable polycarbonate resin, or is a brominated polymer oroligomer, or a brominated flame retardant compound.

Embodiment 3

The composition of any one of Embodiments 1-2, wherein the brominesource is a brominated epoxy oligomer or is a brominated polymer oroligomer having repeating units derived from bisphenol-A andtetrabromobisphenol-A and containing repeating units derived from thetetrabromobisphenol-A in an amount such that the polymer or oligomercontains from about 5 wt % to about 30 wt % of bromine.

Embodiment 4

The composition of any one of Embodiments 1-3, wherein the brominesource is selected from the group consisting of a polybrominateddiphenyl ether (PBDE); hexabromocyclododecane (HBCD);tetrabromobisphenol-A (TTBPA); bis(2,6-dibromophenyl)-methane;2,2-bis-(3-phenyl-4-bromophenyl)-ethane;2,2-bis-(3,5-dibromophenyl)-hexane; bis-(3-nitro-4-bromophenyl)-methane;2,2-bis-(3-bromo-4-hydroxyphenyl)-propane; 1,4-dibromobenzene;2,4′-dibromobiphenyl; and 1,2-bis(tetrabromophthalimido)ethane.

Embodiment 5

The composition of any one of Embodiments 1-4, further comprising fromabout 0.06 wt % to about 0.4 wt % of a non-brominated andnon-chlorinated flame retardant, or further comprising from about 0.04wt % to about 1 wt % of a phosphite stabilizer.

Embodiment 6

The composition of Embodiment 5, wherein the non-brominated andnon-chlorinated flame retardant is potassium perfluorobutane sulfonate(Rimar salt), potassium diphenyl sulfone-3-sulfonate (KSS), or acombination thereof.

Embodiment 7

The composition of any one of Embodiments 1-6, further comprising apolymeric base resin.

Embodiment 8

The composition of Embodiment 7, wherein the weight ratio of thecross-linkable polycarbonate resin to the polymeric base resin is fromabout 10:90 to about 85:15; or wherein the polymeric base resin is abisphenol-A homopolycarbonate.

Embodiment 9

The composition of any one of Embodiments 1-8, wherein the compositionhas a melt flow rate of about 3 to about 19 g/10 minutes at 300° C./1.2kg/360 sec dwell.

Embodiment 10

The composition of any one of Embodiments 1-9, wherein thecross-linkable polycarbonate resin is formed from a reaction of: ahydroxybenzophenone; a first dihydroxy chain extender; and a carbonateprecursor; and optionally a second dihydroxy chain extender; andoptionally an end-capping agent selected from the group consisting ofphenol, p-t-butylphenol, p-cumylphenol, octylphenol, and p-cyanophenol.

Embodiment 11

The composition of Embodiment 10, wherein the hydroxybenzophenone is amonohydroxybenzophenone, and the cross-linkable polycarbonate resincontains from about 0.5 mole % to about 5 mole % of endcap groupsderived from the monohydroxybenzophenone.

Embodiment 12

The composition of Embodiment 11, wherein the monohydroxybenzophenone is4-hydroxybenzophenone; and the first dihydroxy chain extender isbisphenol-A.

Embodiment 13

The composition of Embodiment 10, wherein the hydroxybenzophenone is adihydroxybenzophenone, and the cross-linkable polycarbonate resincontains from about 0.5 mole % to about 50 mole % of repeating unitsderived from the dihydroxybenzophenone.

Embodiment 14

The composition of Embodiment 13, wherein the dihydroxybenzophenone is4,4′-hydroxybenzophenone; and the first dihydroxy chain extender isbisphenol-A.

Embodiment 15

The composition of any one of Embodiments 1-14, wherein thecross-linkable polycarbonate resin is a brominated terpolymer.

Embodiment 16

The composition of any one of Embodiments 1-15, wherein an articlemolded from the composition and having a thickness of 1.2 mm has apFTP(V0) of at least 0.90 after exposure to 36 J/cm² of UVA radiation.

Embodiment 17

An article formed from the composition of any one of Embodiments 1-16.

Embodiment 18

The article of Embodiment 17, wherein the article is a molded article, afilm, a sheet, a layer of a multilayer film, or a layer of a multilayersheet, an automotive bumper, an automotive exterior component, anautomobile mirror housing, an automobile grille, an automobile pillar,an automobile wheel cover, an automobile instrument panel or trim, anautomobile glove box, an automobile door hardware or other interiortrim, an automobile exterior light, an automobile part within the enginecompartment, an agricultural tractor or device part, a constructionequipment vehicle or device part, a construction or agriculturalequipment grille, a marine or personal water craft part, an all-terrainvehicle or all-terrain vehicle part, plumbing equipment, a valve orpump, an air conditioning heating or cooling part, a furnace or heatpump part, a computer part, a computer router, a desk top printer, alarge office/industrial printer, an electronics part, a projector part,an electronic display part, a copier part, a scanner part, an electronicprinter toner cartridge, a hair drier, an iron, a coffee maker, atoaster, a washing machine or washing machine part, a microwave, anoven, a power tool, an electric component, an electric enclosure, alighting part, a dental instrument, a medical instrument, a medical ordental lighting part, an aircraft part, a train or rail part, a seatingcomponent, a sidewall, a ceiling part, cookware, a medical instrumenttray, an animal cage, fibers, a laser welded medical device, fiberoptics, a lense (auto and non-auto), a cell phone part, a greenhousecomponent, a sun room component, a fire helmet, a safety shield, safetyglasses, a gas pump part, a humidifier housing, a thermostat controlhousing, an air conditioner drain pan, an outdoor cabinet, a telecomenclosure or infrastructure, a Simple Network Detection System (SNIDS)device, a network interface device, a smoke detector, a component ordevice in a plenum space, a medical scanner, X-ray equipment, aconstruction or agricultural equipment, a hand held electronic deviceenclosure or part, a walkie-talkie enclosure or part, a scannerenclosure or part, a media/MP3/MP4 player enclosure or part, a radioenclosure or part, a GPS system enclosure or part, an ebook enclosure orpart, a tablet enclosure or part, a wearable electronic device, a smartwatch, a wearable training/tracking device, a wearable activity/sleepmonitoring system, a wearable electronic wristband, electronic glasses,a hand held tool enclosure or part, a smart phone enclosure or part, ora turbine blade.

Embodiment 19

The article of any one of Embodiments 17-18, wherein the article isformed by injection molding, overmolding, co-injection molding,extrusion, multilayer extrusion, rotational molding, blow molding, orthermoforming.

Embodiment 20

The article of any one of Embodiments 17-19, wherein the article isexposed to UV radiation to cause cross-linking of the polymericcomposition.

The present disclosure has been described with reference to exemplaryembodiments. Obviously, modifications and alterations will occur toothers upon reading and understanding the preceding detaileddescription. It is intended that the present disclosure be construed asincluding all such modifications and alterations insofar as they comewithin the scope of the appended claims or the equivalents thereof.

The invention claimed is:
 1. A polymeric composition, comprising: across-linkable polycarbonate resin containing a photoactive groupderived from a benzophenone; and a bromine source present in an amountsuch that the polymeric composition contains from about 0.3 wt % toabout 15 wt % bromine, wherein the cross-linkable polycarbonate resin isformed from a reaction of: the benzophenone which is adihydroxybenzophenone; a first dihydroxy chain extender; and a carbonateprecursor; and optionally a second dihydroxy chain extender; andoptionally an end-capping agent selected from the group consisting ofphenol, p-t-butylphenol, p-cumylphenol, octylphenol, and p-cyanophenol,and the cross-linkable polycarbonate resin contains from about 0.5 mole% to about 50 mole % of repeating units derived from thedihydroxybenzophenone.
 2. The composition of claim 1, wherein thebromine source is the cross-linkable polycarbonate resin, or is abrominated polymer or oligomer, or a brominated flame retardantcompound.
 3. The composition of claim 1, wherein the bromine source is abrominated epoxy oligomer or is a brominated polymer or oligomer havingrepeating units derived from bisphenol-A and tetrabromobisphenol-A andcontaining repeating units derived from the tetrabromobisphenol-A in anamount such that the polymer or oligomer contains from about 5 wt % toabout 30 wt % of bromine.
 4. The composition of claim 1, wherein thebromine source is selected from the group consisting of a polybrominateddiphenyl ether (PBDE); hexabromocyclododecane (HBCD);tetrabromobisphenol-A (TTBPA); bis(2,6-dibromophenyl)-methane;2,2-bis-(3-phenyl-4-bromophenyl)-ethane;2,2-bis-(3,5-dibromophenyl)-hexane; bis-(3-nitro-4-bromophenyl)-methane;2,2-bis-(3-bromo-4-hydroxyphenyl)-propane; 1,4-dibromobenzene;2,4′-dibromobiphenyl; and 1,2-bis(tetrabromophthalimido)ethane.
 5. Thecomposition of claim 1, further comprising from about 0.06 wt % to about0.4 wt % of a non-brominated and non-chlorinated flame retardant, orfurther comprising from about 0.04 wt % to about 1 wt % of a phosphitestabilizer.
 6. The composition of claim 5, wherein the non-brominatedand non-chlorinated flame retardant is potassium perfluorobutanesulfonate (Rimar salt), potassium diphenyl sulfone-3-sulfonate (KSS), ora combination thereof.
 7. The composition of claim 1, further comprisinga polymeric base resin.
 8. The composition of claim 7, wherein theweight ratio of the cross-linkable polycarbonate resin to the polymericbase resin is from about 10:90 to about 85:15; or wherein the polymericbase resin is a bisphenol-A homopolycarbonate.
 9. The composition ofclaim 1, wherein the composition has a melt flow rate of about 3 toabout 19 g/10 minutes at 300° C./1.2 kg/360 sec dwell.
 10. A polymericcomposition, comprising: a cross-linkable polycarbonate resin containinga photoactive group derived from a benzophenone; and a bromine sourcepresent in an amount such that the polymeric composition contains fromabout 0.3 wt % to about 15 wt % bromine, wherein the cross-linkablepolycarbonate resin is formed from a reaction of: the benzophenone; afirst dihydroxy chain extender; and a carbonate precursor; andoptionally a second dihydroxy chain extender; and optionally anend-capping agent selected from the group consisting of phenol,p-t-butylphenol, p-cumylphenol, octylphenol, and p-cyanophenol, whereinthe benzophenone is a monohydroxybenzophenone, and the cross-linkablepolycarbonate resin contains from about 0.5 mole % to about 5 mole % ofendcap groups derived from the monohydroxybenzophenone.
 11. Thecomposition of claim 10, wherein the monohydroxybenzophenone is4-hydroxybenzophenone; and the first dihydroxy chain extender isbisphenol-A.
 12. The composition of claim 1, wherein thedihydroxybenzophenone is 4,4′-dihydroxybenzophenone; and the firstdihydroxy chain extender is bisphenol-A.
 13. A polymeric composition,comprising: a cross-linkable polycarbonate resin containing aphotoactive group derived from a benzophenone; and a bromine sourcepresent in an amount such that the polymeric composition contains fromabout 0.3 wt % to about 15 wt % bromine, wherein the cross-linkablepolycarbonate resin is a brominated terpolymer derived from a reactionof the benzophenone which is a dihydroxybenzophenone, a first dihydroxychain extender, a second dihydroxy chain extender, a carbonateprecursor, and optionally one or more end-capping agents.
 14. Thecomposition of claim 1, wherein an article molded from the compositionand having a thickness of 1.2 mm has a probability of achieving a firsttime V0 pass of at least 0.90 after exposure to 36 J/cm2 of UVAradiation.
 15. An article formed from the composition of claim
 1. 16.The article of claim 15, wherein the article is a molded article, afilm, a sheet, a layer of a multilayer film, or a layer of a multilayersheet, an automotive bumper, an automotive exterior component, anautomobile mirror housing, an automobile grille, an automobile pillar,an automobile wheel cover, an automobile instrument panel or trim, anautomobile glove box, an automobile door hardware or other interiortrim, an automobile exterior light, an automobile part within the enginecompartment, an agricultural tractor or device part, a constructionequipment vehicle or device part, a construction or agriculturalequipment grille, a marine or personal water craft part, an all-terrainvehicle or all-terrain vehicle part, plumbing equipment, a valve orpump, an air conditioning heating or cooling part, a furnace or heatpump part, a computer part, a computer router, a desk top printer, alarge office/industrial printer, an electronics part, a projector part,an electronic display part, a copier part, a scanner part, an electronicprinter toner cartridge, a hair drier, an iron, a coffee maker, atoaster, a washing machine or washing machine part, a microwave, anoven, a power tool, an electric component, an electric enclosure, alighting part, a dental instrument, a medical instrument, a medical ordental lighting part, an aircraft part, a train or rail part, a seatingcomponent, a sidewall, a ceiling part, cookware, a medical instrumenttray, an animal cage, fibers, a laser welded medical device, fiberoptics, a lense (auto and non-auto), a cell phone part, a greenhousecomponent, a sun room component, a fire helmet, a safety shield, safetyglasses, a gas pump part, a humidifier housing, a thermostat controlhousing, an air conditioner drain pan, an outdoor cabinet, a telecomenclosure or infrastructure, a Simple Network Detection System (SNIDS)device, a network interface device, a smoke detector, a component ordevice in a plenum space, a medical scanner, X-ray equipment, aconstruction or agricultural equipment, a hand held electronic deviceenclosure or part, a walkie-talkie enclosure or part, a scannerenclosure or part, a media/MP3/MP4 player enclosure or part, a radioenclosure or part, a GPS system enclosure or part, an ebook enclosure orpart, a tablet enclosure or part, a wearable electronic device, a smartwatch, a wearable training/tracking device, a wearable activity/sleepmonitoring system, a wearable electronic wristband, electronic glasses,a hand held tool enclosure or part, a smart phone enclosure or part, ora turbine blade.
 17. The article of claim 15, wherein the article isformed by injection molding, overmolding, co-injection molding,extrusion, multilayer extrusion, rotational molding, blow molding, orthermoforming.
 18. The article of claim 15, wherein the article isexposed to UV radiation to cause cross-linking of the polymericcomposition.
 19. The composition of claim 13, wherein the cross-linkablepolycarbonate resin comprises: from 0.5 mole % to 50 mol % repeatingunits derived from the dihydroxybenzophenone, from 50 mole % to 99.5mole % repeating units derived from the first dihydroxy chain extender,and from 50 mole % to 99.5 mole % repeating units derived from thesecond dihydroxy chain extender.
 20. The composition of claim 19,wherein the dihydroxybenzophenone is 4,4′-dihydroxybenzophenone, thefirst dihydroxy chain extender is bisphenol A, and the second chainextender is tetrabromobisphenol A.
 21. The composition of claim 1,wherein the cross-linkable polycarbonate resin is a terpolymercomprising from 0.5 mole % to 50 mol % repeating units derived from thedihydroxybenzophenone, from 50 mole % to 99.5 mole % repeating unitsderived from the first hydroxy chain extender, and from 50 mole % to99.5 mole % repeating units derived from the second dihydroxy chainextender.
 22. The composition of claim 21, wherein thedihydroxybenzophenone is 4,4′-dihydroxybenzophenone, the first dihydroxychain extender is bisphenol A, and the second chain extender is selectedfrom the group consisting of sebacic acid, a polysiloxane monomer, and1,1-bis(4-hydroxy-3-methylphenyl) cyclohexane.